JP4456894B2 - Dye-sensitized solar cell laminated film and dye-sensitized solar cell electrode using the same - Google Patents
Dye-sensitized solar cell laminated film and dye-sensitized solar cell electrode using the same Download PDFInfo
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- JP4456894B2 JP4456894B2 JP2004058734A JP2004058734A JP4456894B2 JP 4456894 B2 JP4456894 B2 JP 4456894B2 JP 2004058734 A JP2004058734 A JP 2004058734A JP 2004058734 A JP2004058734 A JP 2004058734A JP 4456894 B2 JP4456894 B2 JP 4456894B2
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- dye
- solar cell
- film
- sensitized solar
- transparent conductive
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- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 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
- 125000003944 tolyl group Chemical group 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
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000037303 wrinkles Effects 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)
- Laminated Bodies (AREA)
- Photovoltaic Devices (AREA)
- Non-Insulated Conductors (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、色素増感型太陽電池を作成した際に、長期間太陽光に暴露しても光発電効率を高く維持することのできる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。 The present invention relates to a laminated film for a dye-sensitized solar cell and an electrode for a dye-sensitized solar cell. More specifically, the processability of the porous semiconductor layer and the adhesion thereof are improved to prepare a dye-sensitized solar cell. In particular, the present invention relates to a dye-sensitized solar cell laminated film that can maintain high photovoltaic power generation efficiency even when exposed to sunlight for a long period of time, and 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。 Dye-sensitized solar cells have been proposed as silicon-based solar cells since a photoelectric conversion element using dye-sensitized semiconductor fine particles was proposed (Nature 353, 737-740, (1991)). It attracts attention as a new solar cell to replace. In particular, a dye-sensitized solar cell 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、ポリエステルフィルム上の透明導電層の表面特性が適当でないと、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非常に困難となり、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, if the surface characteristics of the transparent conductive layer on the polyester film are not appropriate, it is very difficult to ensure the adhesion between the transparent conductive layer and the porous semiconductor layer, and there is a problem that the photovoltaic performance is lowered.
また色素増感型太陽電池では、光（特に紫外線）に励起されて活性となる金属酸化物系半導体を電極材料として用いるため、光増感材として吸着させた色素が劣化し、光発電効率が徐序に低下する問題がある。
これに対して、特開２００３−２１７６９０号公報などでは、紫外線吸収剤を含む樹脂層を塗工により設ける方法が提案されている。
In addition, in a dye-sensitized solar cell, a metal oxide semiconductor that is activated by light (especially ultraviolet rays) is used as an electrode material, so that the dye adsorbed as a photosensitizer deteriorates and the photovoltaic efficiency is improved. There is a problem of gradual decline.
On the other hand, Japanese Patent Application Laid-Open No. 2003-217690 proposes a method of providing a resin layer containing an ultraviolet absorber by coating.
しかしながら、十分な紫外線遮蔽効果を得ようとすると、樹脂層の厚みを厚くする必要があり、技術的に艱難であったり不経済であるとともに、紫外線吸収剤の吸収波長が可視光にかかる場合には、光発電効率が低下するという問題がある。 However, in order to obtain a sufficient ultraviolet shielding effect, it is necessary to increase the thickness of the resin layer, which is technically difficult or uneconomical, and the absorption wavelength of the ultraviolet absorber is applied to visible light. However, there is a problem that the photovoltaic efficiency is lowered.
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、耐久性を有しながら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、積層ポリエステルフィルムおよび電極を提供することを目的とする。 The present invention solves such problems of the prior art, is excellent in adhesion between the transparent conductive layer and the porous semiconductor layer, and can create a dye-sensitized solar cell with high photovoltaic performance while having durability, An object is to provide a laminated polyester film and an electrode.
すなわち本発明は、波長３７０ｎｍでの光線透過率が３％以下かつ４００ｎｍでの光線透過率が７０％以上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以上であることを特徴とする、色素増感型太陽電池用積層フィルムである。 That is, the present invention comprises a polyester film having a light transmittance of 3% or less at a wavelength of 370 nm and a light transmittance of 400% or more at 400 nm, and a transparent conductive layer provided on one side thereof, and the surface of the transparent conductive layer A laminated film for a dye-sensitized solar cell, wherein the tension is 40 mN / m or more.
以下、本発明を詳細に説明する。
[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。
Hereinafter, the present invention will be described in detail.
[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。 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.
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 to deactivate the transesterification catalyst before the polymerization reaction. However, the content in polyethylene-2,6-naphthalenedicarboxylate as the phosphorus element is preferably 20 to 100 ppm from the viewpoint of the 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を構成するポリエステルには、フィルムにおける波長３７０ｎｍおよび４００ｎｍの光線透過率を調整するために、紫外線吸収剤を含有させることが好ましい。この紫外線吸収剤は、その種類を特に特定されないが、下記式（I） In order to adjust the light transmittance at wavelengths of 370 nm and 400 nm in the film, the polyester constituting the polyester film in the present invention preferably contains an ultraviolet absorber. The type of this ultraviolet absorber is not particularly specified, but the following formula (I)
で表わされる環状イミノエステル及び下記式（II）
And a cyclic imino ester represented by the following formula (II)
下記式（II）-ｂ
で表わされる環状イミノエステルから選ばれる少なくとも１種の化合物を、未反応の形態で用いるのが好ましい。
It is preferable to use at least one compound selected from cyclic iminoesters represented by the formula in an unreacted form.
かかる環状イミノエステルは紫外線吸収剤として公知の化合物であり、例えば特開昭５９−１２９５２号公報に記載されている。 Such a cyclic imino ester is a compound known as an ultraviolet absorber and is described, for example, in JP-A-59-12952.
前記一般式（Ｉ）中、Ｘ1は式（Ｉ）に表わされたＸ1からの２本の結合手が1位、２位の位置関係にある２価の芳香族残基であり；ｎは１、２又は３であり；Ｒ1はｎ価の炭化水素残基で、これは更にヘテロ原子を含有していてもよい、又はＲ1はｎ＝２のとき直接結合であることができる。
Ｘ1としては、好ましくは例えば１，２−フェニレン、１，２−ナフチレン、２，３−ナフチレン、下記式
In the general formula (I), X 1 is a divalent aromatic residue in which two bonds from X 1 represented by the formula (I) are in the 1-position and 2-position positional relationship; n is 1, 2 or 3; R 1 is an n-valent hydrocarbon residue, which may further contain heteroatoms, or R 1 may be a direct bond when n = 2 it can.
X 1 is preferably 1,2-phenylene, 1,2-naphthylene, 2,3-naphthylene, or the following formula:
で表わされる基を挙げることができる。これらのうち、特に１，２−フェニレンが好ましい。
The group represented by these can be mentioned. Of these, 1,2-phenylene is particularly preferable.
Ｘ1について例示した上記芳香族残基は、例えば炭素数１〜１０のアルキル例えばメチル、エチル、プロピル、ヘキシル、デシル等；炭素数６〜１２のアリール例えばフェニル、ナフチル等；炭素数５〜１２のシクロアルキル例えばシクロペンチル、シクロヘキシル等；炭素数８〜２０のアラルキル例えばフェニルエチル等；炭素数１〜１０のアルコキシ例えばメトキシ、エトキシ、デシルオキシ等；ニトロ；ハロゲン例えば塩素、臭素等；炭素数２〜１０のアシル例えばアセチル、プロポニル、ゼンゾイル、デカノイル等；などの置換基で置換されていてもよい。好ましくは、３−メチル−１，２−フェニレン、３−クロロ−１，２−フェニレンを挙げることができる。 The aromatic residue exemplified for X 1 is, for example, alkyl having 1 to 10 carbon atoms such as methyl, ethyl, propyl, hexyl, decyl, etc .; aryl having 6 to 12 carbon atoms such as phenyl, naphthyl, etc .; Cycloalkyl such as cyclopentyl, cyclohexyl, etc .; aralkyl having 8 to 20 carbon atoms such as phenylethyl; alkoxy having 1 to 10 carbon atoms such as methoxy, ethoxy, decyloxy, etc .; nitro; halogen such as chlorine, bromine and the like; And may be substituted with a substituent such as acetyl, proponyl, zenzoyl, decanoyl, etc. Preferable examples include 3-methyl-1,2-phenylene and 3-chloro-1,2-phenylene.
Ｒ1はｎ価（ただし、ｎは１、２又は３である）の炭化水素残基であるか、又はｎが２であるときに限り直接結合であることができる。 R 1 is an n-valent hydrocarbon residue (where n is 1, 2 or 3) or can be a direct bond only when n is 2.
１価の炭化水素残基（ｎ＝１の場合）としては、第一に、例えば炭素数１〜１０の未置換脂肪族基、炭素数６〜１２の未置換芳香族基、炭素数５〜１２の未置換脂環族基が挙げられる。 As the monovalent hydrocarbon residue (when n = 1), first, for example, an unsubstituted aliphatic group having 1 to 10 carbon atoms, an unsubstituted aromatic group having 6 to 12 carbon atoms, or 5 to 5 carbon atoms. 12 unsubstituted alicyclic groups.
炭素数１〜１０の未置換脂肪族基としては、例えばメチル、エチル、プロピル、ヘキシル、デシル等を、炭素数６〜１２の未置換芳香族基としては、例えばフェニル、ナフチル、ビフェニル等を；炭素数５〜１２の未置換脂環族基としては、例えばシクロペンチル、シクロヘキシル等を挙げることができる。
また、上記１価の炭化水素残基としては、第二に、例えば下記式（ｃ）
Examples of the unsubstituted aliphatic group having 1 to 10 carbon atoms include methyl, ethyl, propyl, hexyl, and decyl. Examples of the unsubstituted aromatic group having 6 to 12 carbon atoms include phenyl, naphthyl, and biphenyl; Examples of the unsubstituted alicyclic group having 5 to 12 carbon atoms include cyclopentyl and cyclohexyl.
As the monovalent hydrocarbon residue, secondly, for example, the following formula (c)
で表わされる基、下記式（ｄ）
A group represented by formula (d):
で表わされる基、下記式（ｅ）
A group represented by the following formula (e):
で表わされる基、下記式（ｆ）
A group represented by formula (f)
で表わされる置換された脂肪族残基又は芳香族残基を挙げることができる。
The substituted aliphatic residue or aromatic residue represented by these can be mentioned.
また、上記１価の炭化水素残基としては、第三に、上記未置換の芳香族残基が例えば上記Ｘ1を表わす芳香族残基の置換基として例示したと同じ置換基で置換されているものを挙げることができる。それ故、かかる置換基で置換された場合の例としては、例えばトリル、メチルナフチル、ニトロフェニル、ニトロナフチル、クロロフェニル、ベンゾイルフェニイル、アセチルフェニル又はアセチルナフチル等を挙げることができる。 Further, as the monovalent hydrocarbon residue, thirdly, the unsubstituted aromatic residue is substituted with the same substituent as exemplified as the substituent of the aromatic residue representing X 1 , for example. You can list what you have. Therefore, examples of substitution with such a substituent include tolyl, methylnaphthyl, nitrophenyl, nitronaphthyl, chlorophenyl, benzoylphenyl, acetylphenyl, and acetylnaphthyl.
１価の炭化水素残基としては、上記式（ｃ）、（ｄ）、（ｅ）又は（ｆ）で表わされる基、すなわち置換された脂肪族残基又は芳香族残基、特にそのうち置換された芳香族残基が好ましい。 As the monovalent hydrocarbon residue, a group represented by the above formula (c), (d), (e) or (f), that is, a substituted aliphatic residue or aromatic residue, in particular, a substituted one thereof. Aromatic residues are preferred.
２価の炭化水素残基（ｎ＝２の場合）としては、第一に、例えば２価の、炭素数２〜１０の未置換の脂肪族残基、炭素数６〜１２の未置換の芳香族残基、炭素数５〜１２の未置換の脂環族残基基が挙げられる。 As the divalent hydrocarbon residue (when n = 2), first, for example, a divalent, unsubstituted aliphatic residue having 2 to 10 carbon atoms, or an unsubstituted aromatic having 6 to 12 carbon atoms is used. Group residues and unsubstituted alicyclic residue groups having 5 to 12 carbon atoms.
２価の炭素数２〜１０の未置換の脂肪族基としては、例えばエチレン、トリメチレン、テトラメチレン、デカメチレン等を、２価の炭素数６〜１２の未置換の芳香族残基としては、例えばフェニレン、ナフチレン、Ｐ，Ｐ’−ビフェニレン等を；２価の炭素数５〜１２の未置換の脂環族残基としては、例えばシクロペンチレン、シクロヘキシレン等を挙げることができる。
また、上記２価の炭化水素残基としては、第二に、例えば下記式（ｇ）
Examples of the divalent unsubstituted aliphatic group having 2 to 10 carbon atoms include ethylene, trimethylene, tetramethylene, decamethylene and the like. Examples of the divalent unsubstituted aromatic residue having 6 to 12 carbon atoms include, for example, Examples of the divalent unsubstituted alicyclic residue having 5 to 12 carbon atoms include cyclopentylene and cyclohexylene.
As the above divalent hydrocarbon residue, secondly, for example, the following formula (g)
で表わされる基、又は下記式（ｈ）
Or a group represented by the following formula (h)
で表わされる、置換された脂肪族残基又は芳香族残基を挙げることができる。
The substituted aliphatic residue or aromatic residue represented by these can be mentioned.
また、上記２価の炭化水素残基としては、第三に、上記未置換の２価の芳香族残基が、例えば上記Ｘ1を表わす芳香族基の置換基として例示したと同じ置換基で置換されているものを挙げることができる。 In addition, as the divalent hydrocarbon residue, thirdly, the unsubstituted divalent aromatic residue is, for example, the same substituent as exemplified as the substituent of the aromatic group representing X 1 above. Mention may be made of substituted ones.
ｎが２の場合には、Ｒ1としては、これらのうち直接結合又は上記第一〜第三の群の未置換又は置換された２価の芳香族炭化水素残基が好ましく、特に２本の結合手が最も離れた位置から出ている第一又は第三の群の未置換又は置換された芳香族炭化水素残基が好ましく、就中Ｐ−フェニレン、Ｐ，Ｐ’−ビフェニレン又は２，６−ナフチレンが好ましい。 When n is 2, R 1 is preferably a direct bond or an unsubstituted or substituted divalent aromatic hydrocarbon residue of the first to third groups, particularly two Preferred are the first or third group of unsubstituted or substituted aromatic hydrocarbon residues with the bond coming from the furthest position, especially P-phenylene, P, P′-biphenylene or 2,6 Naphthylene is preferred.
３価の炭化水素残基（ｎ＝３の場合）としては、例えば３価の炭素数６〜１２の芳香族残基を挙げることができる。
かかる芳香族残基としては、例えば
Examples of the trivalent hydrocarbon residue (when n = 3) include a trivalent aromatic residue having 6 to 12 carbon atoms.
Examples of such aromatic residues include:
かかる芳香族残基は、上記１価の芳香族残基の置換基として例示したと同じ置換基で置換されていてもよい。
上記一般式（Ｉ）中、Ｒ2およびＲ3は同一もしくは異なり１価の炭化水素残基であり、Ｘ2は４価の芳香族炭化水素残基である。
Ｒ2およびＲ3としては、上記式（Ｉ）の説明において、ｎ＝１の場合のＲ1について例示したと同じ基を例として挙げることができる。
４価の芳香族炭化水素残基としては、例えば
Such an aromatic residue may be substituted with the same substituent as exemplified as the substituent of the monovalent aromatic residue.
In the general formula (I), R 2 and R 3 are the same or different and are monovalent hydrocarbon residues, and X 2 is a tetravalent aromatic hydrocarbon residue.
Examples of R 2 and R 3 include the same groups as those exemplified for R 1 in the case of n = 1 in the description of the above formula (I).
Examples of tetravalent aromatic hydrocarbon residues include:
で表わされる基を挙げることができる。
The group represented by these can be mentioned.
上記４価の芳香族残基は、上記式（Ｉ）の説明において、Ｒ1を表わす１価の芳香族残基の置換基として例示したと同じ置換基で置換されていてもよい。 The tetravalent aromatic residue may be substituted with the same substituent as exemplified as the substituent of the monovalent aromatic residue representing R 1 in the description of the formula (I).
本発明において用いられる上記式（Ｉ）および（II）で表わされる環状イミノエステルの具体例としては、例えば下記の化合物を挙げることができる。 Specific examples of the cyclic imino ester represented by the above formulas (I) and (II) used in the present invention include the following compounds.
上記式（Ｉ）の化合物
ｎ＝１の場合の化合物
２−メチル−３，１−ベンゾオキサジン−４−オン、２−ブチル−３，１−ベンゾオキサジン−４−オン、２−フェニル−３，１−ベンゾオキサジン−４−オン、２−（１−又は２−ナフチル）−３，１−ベンゾオキサジン−４−オン、２−（４−ビフェニル）−３，１−ベンゾオキサジン−４−オン、２−ｐ−ニトロフェニル−３，１−ベンゾオキサジン−４−オン、２−ｍ−ニトロフェニル−３，１−ベンゾオキサジン−４−オン、２−ｐ−ベンゾイルフェニル−３，１−ベンゾオキサジン−４−オン、２−ｐ−メトキシフェニル−３，１−ベンゾオキサジン−４−オン、２−ｏ−メトキシフェニル−３，１−ベンゾオキサジン−４−オン、２−シクロヘキシル−３，１−ベンゾオキサジン−４−オン、２−ｐ−（又はｍ−）フタルイミドフェニル−３，１−ベンゾオキサジン−４−オン、N−フェニル−４−（３，１−ベンゾオキサジン−４−オン−２−イル）フタルイミド、N−ベンゾイル−４−（３，１−ベンゾオキサジン−４−オン−２−イル）アニリン、N−ベンゾイル−N−メチル−４−（３，１−ベンゾオキサジン−４−オン−２−イル）アニリン、２−（ｐ−（N−メチルカルボニル）フェニル）−３，１−ベンゾオキサジン−４−オン。
Compound of the above formula (I) Compound when n = 1 2-Methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3, 1-benzoxazin-4-one, 2- (1- or 2-naphthyl) -3,1-benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3,1-benzoxazine- 4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazine 4-one, 2-p- (or m-) phthalimidophenyl-3,1-benzoxazin-4-one, N-phenyl-4- (3,1-benzoxazin-4-one-2-yl) phthalimide N-benzoyl-4- (3,1-benzoxazin-4-one-2-yl) aniline, N-benzoyl-N-methyl-4- (3,1-benzoxazin-4-on-2-yl) ) Aniline, 2- (p- (N-methylcarbonyl) phenyl) -3,1-benzoxazin-4-one.
ｎ＝２の場合の化合物
２，２’−ビス（３，１−ベンゾオキサジン−４−オン）、２，２’−エチレンビス（３，１−ベンゾオキサジン−４−オン）、２，２’−テトラメチレンビス（３，１−ベンゾオキサジン−４−オン）、２，２’−デカメチレンビス（３，１−ベンゾオキサジン−４−オン）、２，２’−ｐ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）、２，２’−ｐ−フェニレンビス（６−メチル−３，１−ベンゾオキサジン−４−オン）、２，２’−ｐ−フェニレンビス（６−クロロ−３，１−ベンゾオキサジン−４−オン）、２，２’−ｍ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）、２，２’−（４，４’−ジフェニレン）ビス（３，１−ベンゾオキサジン−４−オン）、２，２’−（２，６−又は１，５−ナフチレン）ビス（３，１−ベンゾオキサジン−４−オン）、２，２’−（２−メチル-ｐ-フェニレン）ビス（３，１−ベンゾオキサジン−４−オン）、２，２’−（２−ニトロ−ｐ−フェニレン）ビス（３，１−ベンゾオキサジン−４−オン）、２，２’−（２−クロロ−ｐ−フェニレン）ビス（３，１−ベンゾオキサジン−４−オン）、２，２’−（１，４−シクロヘキシレン）ビス（３，１−ベンゾオキサジン−４−オン）、N−ｐ−（３，１−ベンゾオキサジン−４−オン−２−イル）フェニル、４−（３，１−ベンゾオキサジン−４−オン−２−イル）フタルイミド、N−ｐ−（３，１−ベンゾオキサジン−４−オン−２−イル）ベンゾイル、４−（３，１−ベンゾオキサジン−４−オン−２−イル）アニリン。
Compounds when n = 2 2,2′-bis (3,1-benzoxazin-4-one), 2,2′-ethylenebis (3,1-benzoxazin-4-one), 2,2 ′ -Tetramethylenebis (3,1-benzoxazin-4-one), 2,2'-decamethylenebis (3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (3 1-benzoxazin-4-one), 2,2′-p-phenylenebis (6-methyl-3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (6-chloro-) 3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3 , 1-Benzoxazin-4-one), 2,2 ′-(2,6- or 1,5-na Tylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-( 2-nitro-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2-chloro-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(1,4-cyclohexylene) bis (3,1-benzoxazin-4-one), Np- (3,1-benzoxazin-4-one-2-yl) phenyl, 4 -(3,1-benzoxazin-4-on-2-yl) phthalimide, Np- (3,1-benzoxazin-4-on-2-yl) benzoyl, 4- (3,1-benzoxazine -4-On-2-yl) aniline.
ｎ＝３の場合の化合物
１，３，５−トリ（３，１−ベンゾオキサジン−４−オン−２−イル）ベンゼン、１，３，５−トリ（３，１−ベンゾオキサジン−４−オン−２−イル）ナフタレン、２，４，６−トリ（３，１−ベンゾオキサジン−４−オン−２−イル）ナフタレン
Compounds when n = 3 1,3,5-tri (3,1-benzoxazin-4-one-2-yl) benzene, 1,3,5-tri (3,1-benzoxazin-4-one) -2-yl) naphthalene, 2,4,6-tri (3,1-benzoxazin-4-one-2-yl) naphthalene
上記式(II)の化合物
２，８−ジメチル−４H，６H−ベンゾ（１，２−ｄ；５，４−ｄ’）ビス（１，３）−オキサジン−４，６−ジオン、２，７−ジメチル−４H，９H−ベンゾ（１，２−ｄ；４，５−ｄ’）ビス（１，３）−オキサジン−４，９−ジオン、２，８−ジフェニル−４H，８H−ベンゾ（１，２−ｄ；５，４−ｄ’）ビス（１，３）−オキサジン−４，６−ジオン、２，７−ジフェニル−４H，９H−ベンゾ（１，２−ｄ；４，５−ｄ’）ビス（１，３）−オキサジン−４，６−ジオン、６，６’−ビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−ビス（２−エチル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−ビス（２−フェニル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−メチレンビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−メチレンビス（２−フェニル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−エチレンビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−エチレンビス（２−フェニル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−ブチレンビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−ブチレンビス（２−フェニル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−オキシビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−オキシビス（２−フェニル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−スルホニルビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−スルホニルビス（２−フェニル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−カルボニルビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、６，６’−カルボニルビス（２−フェニル−４H，３，１−ベンゾオキサジン−４−オン）、７，７’−メチレンビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、７，７’−メチレンビス（２−フェニル−４H，３，１−ベンゾオキサジン−４−オン）、７，７’−ビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、７，７’−エチレンビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、７，７’−オキシビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、７，７’−スルホニルビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、７，７’−カルボニルビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、６，７’−ビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、６，７’−ビス（２−フェニル−４H，３，１−ベンゾオキサジン−４−オン）、６，７’−メチレンビス（２−メチル−４H，３，１−ベンゾオキサジン−４−オン）、６，７’−メチレンビス（２−フェニル−４H，３，１−ベンゾオキサジン−４−オン）。
Compound of the above formula (II) 2,8-dimethyl-4H, 6H-benzo (1,2-d; 5,4-d ′) bis (1,3) -oxazine-4,6-dione, 2,7 -Dimethyl-4H, 9H-benzo (1,2-d; 4,5-d ') bis (1,3) -oxazine-4,9-dione, 2,8-diphenyl-4H, 8H-benzo (1 , 2-d; 5,4-d ′) bis (1,3) -oxazine-4,6-dione, 2,7-diphenyl-4H, 9H-benzo (1,2-d; 4,5-d ') Bis (1,3) -oxazine-4,6-dione, 6,6'-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-bis (2 -Ethyl-4H, 3,1-benzoxazin-4-one), 6,6'-bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-methylenebi (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6′-ethylene Bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-ethylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6 ′ -Butylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-butylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6 ' -Oxybis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-oxybis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6 ' -Sulfonylbis (2-methyl-4H, 3,1-benzoxazi 4-one), 6,6′-sulfonylbis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6′-carbonylbis (2-methyl-4H, 3,1) -Benzoxazin-4-one), 6,6'-carbonylbis (2-phenyl-4H, 3,1-benzoxazin-4-one), 7,7'-methylenebis (2-methyl-4H, 3, 1-benzoxazin-4-one), 7,7′-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 7,7′-bis (2-methyl-4H, 3, 1-benzoxazin-4-one), 7,7′-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-oxybis (2-methyl-4H, 3) , 1-Benzoxazin-4-one), 7,7′-sulfonylbis (2- Til-4H, 3,1-benzoxazin-4-one), 7,7′-carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7′-bis (2 -Methyl-4H, 3,1-benzoxazin-4-one), 6,7'-bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,7'-methylenebis (2 -Methyl-4H, 3,1-benzoxazin-4-one), 6,7'-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one).
上記例示化合物のうち、上記式（I)の化合物、より好ましくはｎ＝２の場合の上記式（Ｉ）の化合物、特に好ましくは下記式（Ｉ）-１ Of the above exemplified compounds, the compound of the above formula (I), more preferably the compound of the above formula (I) when n = 2, particularly preferably the following formula (I) -1
で表わされる化合物が有利に用いられる。
Are preferably used.
式（Ｉ）-１の化合物としては、就中２，２’−ｐ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）、２，２’−ｐ−フェニレンビス（６−メチル−３，１−ベンゾオキサジン−４−オン）、２，２’−ｐ−フェニレンビス（６−クロロ−３，１−ベンゾオキサジン−４−オン）、２，２’−（４，４’−ジフェニレン）ビス（３，１−ベンゾオキサジン−４−オン）および２，２’−（２，６−ナフチレン）ビス（３，１−ベンゾオキサジン−４−オン）が好ましい。 Among the compounds of formula (I) -1, are 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (6-methyl-3), among others. , 1-benzoxazin-4-one), 2,2′-p-phenylenebis (6-chloro-3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) Bis (3,1-benzoxazin-4-one) and 2,2 ′-(2,6-naphthylene) bis (3,1-benzoxazin-4-one) are preferred.
これら環状イミノエステルの紫外線吸収特性は、例えばその代表的化合物について特開昭５９−１２９５２号公報に記載されているので、それを援用する。 The ultraviolet absorption characteristics of these cyclic imino esters are described in, for example, Japanese Patent Application Laid-Open No. 59-12952 for representative compounds thereof, which are incorporated herein by reference.
前記環状イミノエステルは、ポリエステルに対して優れた相溶性を有するが、前記特開昭５９−１２９５２号公報や米国特許第４２９１１５２号明細書に記載されているように、ポリエステルの末端水酸基と反応する能力を有する。そこで、環状イミノエステルが実質的に未反応な状態で含有されるように、環状イミノエステルとポリエステルとを注意深く混合させることが求められる。ただし、ポリエステルとして、主たる割合の末端基がカルボキシル基であるポリエステルや、末端水酸基が該環状イミノエステルと反応性の無い末端封鎖剤で封鎖されているポリエステルを用いる場合、環状イミノエステルを未反応の状態で含有する組成物を製造するのに特別の注意を払う必要は無い。末端基の主たる割合が水酸基であるポリエステルを用いる場合には、溶融混合の時間は、下記式 The cyclic imino ester has excellent compatibility with the polyester, but reacts with the terminal hydroxyl group of the polyester as described in JP-A-59-12952 and US Pat. No. 4,291,152. Have the ability. Therefore, it is required to carefully mix the cyclic imino ester and the polyester so that the cyclic imino ester is contained in a substantially unreacted state. However, when a polyester in which the main proportion of the terminal group is a carboxyl group or a polyester in which the terminal hydroxyl group is blocked with a terminal blocking agent that is not reactive with the cyclic imino ester is used as the polyester, the cyclic imino ester is unreacted. No special care needs to be taken to produce the composition containing in the state. When using a polyester in which the main proportion of terminal groups is a hydroxyl group, the melt mixing time is expressed by the following formula:
［数１］
Logｔ≦−０．００８Ｔ＋４．８
及び
［数２］
Ｔｍ＜Ｔ＜３２０
（式中、ｔは溶融混合時間（秒）、Ｔは溶融混合温度（℃）及びＴｍはポリエステルの溶融温度（℃）である。）
を満足するように、短時間で完了するようにするのが望ましい。この場合、環状イミノエステルとポリエステルとが少しの割合で反応する可能性があるが、この反応によってポリエステルの分子量は大きくなるので、この割合によっては可視光吸収剤によるポリエステルの劣化による分子量低下を防ぐことが可能である。なお、環状イミノエステルがポリエステルと反応した場合、紫外線吸収波長領域が、一般に、未反応の状態の紫外線吸収波長領域より低波長側にずれる傾向を示し、それ故高波長側の紫外線を透過する傾向をもつ。
[Equation 1]
Logt ≦ −0.008T + 4.8
And [Equation 2]
Tm <T <320
(In the formula, t is the melt mixing time (second), T is the melt mixing temperature (° C.), and Tm is the melting temperature (° C.) of the polyester.)
It is desirable to complete in a short time so as to satisfy the above. In this case, there is a possibility that the cyclic imino ester and the polyester react with each other at a small ratio, but this reaction increases the molecular weight of the polyester, and depending on this ratio, the molecular weight decrease due to degradation of the polyester by the visible light absorber is prevented. It is possible. When a cyclic imino ester reacts with polyester, the ultraviolet absorption wavelength region generally tends to shift to a lower wavelength side than the unreacted ultraviolet absorption wavelength region, and therefore tends to transmit ultraviolet light on the higher wavelength side. It has.
前記環状イミノエステルは、適量を添加する場合、昇華物が殆どないので、製膜でダイ周辺を汚すことが少なく好ましい。 When the appropriate amount is added, the cyclic imino ester is preferable because it hardly causes sublimation, so that the periphery of the die is not soiled by film formation.
前記紫外線吸収剤の添加量は、ポリエステル樹脂の光吸収特性にもよるが、ポリエステル樹脂に対し、０．１〜５重量％が好ましく、さらには０．２〜３重量％が好ましい。この量が０．１％未満では波長３７０ｎｍの光線透過率を十分に下げることができないことがあり、一方５重量％を超えると波長４００ｎｍの光線透過率が十分に高められない場合があり、好ましくない。 Although the addition amount of the said ultraviolet absorber is based also on the light absorption characteristic of a polyester resin, 0.1 to 5 weight% is preferable with respect to a polyester resin, Furthermore, 0.2 to 3 weight% is preferable. If this amount is less than 0.1%, the light transmittance at a wavelength of 370 nm may not be sufficiently lowered. On the other hand, if it exceeds 5% by weight, the light transmittance at a wavelength of 400 nm may not be sufficiently increased. Absent.
前記紫外線吸収剤のポリエステルへの添加方法は特に限定されないが、ポリエステル重合工程、フィルム製膜前の溶融工程でのポリマー中への練込み、二軸延伸フィルムへの含浸、などを挙げることができ、特にポリエステル重合度低下を防止する意味でもフィルム製膜前の溶融工程でのポリマー中への練込みが好ましい。その際、紫外線吸収剤の練込みは、化合物粉体の直接添加法、マスターバッチ法などにより行うことができる。 The method for adding the ultraviolet absorber to the polyester is not particularly limited, and examples thereof include a polyester polymerization step, kneading into a polymer in a melting step before film formation, and impregnation into a biaxially stretched film. In particular, kneading into the polymer in the melting step before film formation is also preferred in order to prevent a decrease in the degree of polymerization of the polyester. At that time, the kneading of the ultraviolet absorber can be performed by a direct addition method of a compound powder, a master batch method or the like.
本発明においては、ポリエステルフィルムの波長３７０ｎｍにおける光線透過率は３％以下、より好ましくは２％以下、波長４００ｎｍにおける光線透過率は７０％以上、より好ましくは７５％以上である。波長３７０ｎｍにおける光線透過率が３％を超えると紫外線遮蔽効果が不十分となり、色素増感型太陽電池を作成した場合に経時による光発電効率の低下がみられる。一方、波長４００ｎｍにおける光線透過率が７０％未満であると、光発電に寄与する可視光量が低下するために、十分な光発電効率を得られなくなる。 In the present invention, the light transmittance of the polyester film at a wavelength of 370 nm is 3% or less, more preferably 2% or less, and the light transmittance at a wavelength of 400 nm is 70% or more, more preferably 75% or more. When the light transmittance at a wavelength of 370 nm exceeds 3%, the ultraviolet shielding effect becomes insufficient, and when a dye-sensitized solar cell is produced, the photovoltaic power generation efficiency decreases with time. On the other hand, if the light transmittance at a wavelength of 400 nm is less than 70%, the visible light amount contributing to the photovoltaic power generation is reduced, so that sufficient photovoltaic power generation efficiency cannot be obtained.
本発明におけるポリエステルフィルムは、２００℃で１０分処理した際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好ましくは０．８％以下、さらに好ましくは０．５％以下、特に好ましくは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り好ましくない。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％以上０．５％以下、更に好ましくは０％以上０．３％以下である。 In the polyester film of the present invention, the absolute value of the difference in heat shrinkage between the longitudinal direction and the width direction of the film when treated at 200 ° C. for 10 minutes is preferably 0.8% or less, more preferably 0.5% or less, Particularly preferably, it is 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. Is not preferable. The heat shrinkage rate in the longitudinal direction of the film should be small, preferably 0% or more and 0.5% or less, and more preferably 0% or more and 0.3% or less.
本発明において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１．５％以下であることが好ましい。さらに好ましいヘーズ値は１．０％以下、特に好ましくは０．５％以下である。 In the present invention, the polyester film preferably has a haze value of 1.5% or less in order to perform photovoltaic power generation more efficiently. A more preferred haze value is 1.0% or less, particularly preferably 0.5% or less.
本発明におけるポリエステルフィルムの３次元中心線平均粗さは、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、さらに好ましくは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 three-dimensional centerline average roughness of the polyester film in the present invention is preferably 0.0001 to 0.02 μm on both sides, more preferably 0.0001 to 0.015 μm, and more preferably 0.0001 to 0.010 μm. is there. In particular, it is preferable that the average roughness of at least one side of the three-dimensional center line 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１０〜５００μｍであることが好ましく、より好ましくは２０〜４００μｍ、更に好ましくは５０〜３００μｍである。 It is preferable that the thickness of the polyester film in this invention is 10-500 micrometers, More preferably, it is 20-400 micrometers, More preferably, it is 50-300 micrometers.
次に、本発明における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 in 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 form, cooled and solidified with a casting drum to form an unstretched film, and this unstretched film is once or twice or more in the longitudinal direction at Tg to (Tg + 60) ° C. 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 a film in a suspended state as disclosed in JP-A-1-275031 can be used.
[透明導電膜]
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）、炭素材料などが用いられる。この導電層は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１００Ω／□以下が好ましく、更に好ましくは４０Ω／□以下である。
[Transparent conductive film]
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. This conductive layer may be a laminate or composite of two or more types, 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。これより薄いと十分に表面抵抗値を低くすることができず、厚い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 thinner than this, the surface resistance value cannot be lowered sufficiently, and if it is thicker, 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、を用いることができる。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 performing corona treatment or plasma treatment. 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１０ｎｍ以上、２００ｎｍ以下であることが好ましく、２０ｎｍ以上、１５０ｎｍ以下であることがより好ましい。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る。
[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 nm or more and 200 nm or less, and more preferably 20 nm or more and 150 nm or less. 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 applying 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、具体的にはポリエステル樹脂、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などが例示できる。これらの樹脂は単独、または２種以上の混合物として用いることができる。 As the constituent material of the easy-adhesion layer, it exhibits excellent adhesion to both the polyester film and the transparent conductive layer. Specifically, polyester resin, acrylic resin, urethane acrylic resin, silicon acrylic resin, melamine resin, polysiloxane Resin etc. can be illustrated. These resins can be used alone or as a mixture of two or more.
[ハードコート]
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は、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アルミナ、シリカ、マイカ等の無機粒子の混合物などが例示できる。ハードコート層の厚みは０．０１〜２０μｍであることが好ましく、特に１〜１０μｍであることが好ましい。
[Hard coat]
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. The method of providing a hard coat layer is preferably a method of coating on a polyester film provided with an easy adhesion layer. 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 a resin component such as a resin and a mixture of these with inorganic particles such as alumina, silica and mica. The thickness of the hard coat layer is preferably from 0.01 to 20 μm, particularly preferably from 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。該反射防止層には、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く採用される。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. For the antireflection layer, a method in which a material having a refractive index different from that of the polyester film is formed in a single layer or two or more layers is preferably employed. 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、好ましい例としては、ＣａＦ2，ＭｇＦ2，ＮａＡｌＦ4，ＳｉＯ2，ＴｈＦ4，ＺｒＯ2，Ｎｄ2Ｏ3，ＳｎＯ2，ＴｉＯ2，ＣｅＯ2，ＺｎＳ，Ｉｎ2Ｏ3などの誘電体が挙げられる。 As a material constituting such an antireflection treatment layer, any material that satisfies the above-described refractive index relationship may be used regardless of whether it is an organic material or an inorganic material. Preferred examples include CaF 2 , MgF 2 , Examples of the dielectric include NaAlF 4 , SiO 2 , ThF 4 , ZrO 2 , Nd 2 O 3 , SnO 2 , TiO 2 , CeO 2 , ZnS, and In 2 O 3 .
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]
本発明における色素増感型太陽電池用電極は、該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）であり、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 dye-sensitized solar cell electrode in the present invention is formed by laminating a porous semiconductor layer on the transparent conductive layer of the laminated film. Examples of the semiconductor material constituting the porous semiconductor layer include titanium oxide (TiO 2 ), zinc oxide (ZnO), and tin oxide (SnO 2 ), which are n-type semiconductors. Materials 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５〜１００ｎｍ、特に５〜５０ｎｍのものが好ましい。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 semiconductor are sintered or fused, and the average particle size of primary particles is 5 to 100 nm, particularly 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).
多孔質半導体層の形成方法に特に限定はないが、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のが好ましい。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、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などを用いることができる。 The method for forming the porous semiconductor layer is not particularly limited, but for example, a coating method, that is, a dispersion containing the porous semiconductor is applied onto the transparent conductive layer of the laminated film and dried by heating to support the porous layer. It is preferable to immobilize it on top. At this time, in order to adjust the dispersion of semiconductor fine particles, in addition to the sol-gel method described above, a method of precipitating fine particles as a coprecipitation product of a chemical reaction in a solvent, ultrasonic irradiation or mechanical pulverization to form ultrafine particles. A 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、１７０℃以上、２５０℃以下、好ましくは１８０℃以上、２３０℃以下、更に好ましくは１９０℃以上、２２０℃以下で加熱処理を施すことが好ましい。１７０℃以上、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。 170 ° C. or higher and 250 ° C. or lower, preferably 180 ° C. or higher and 230 ° C. or lower, in order to reinforce the electronic contact between the semiconductor fine particles and improve the adhesion to the support for the layer of semiconductor fine particles applied. More preferably, the heat treatment is performed at 190 ° C. or higher and 220 ° C. or lower. By performing the heat treatment at 170 ° C. or higher and 250 ° C. or lower, the resistance increase of the porous semiconductor layer can be reduced 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１〜３０μｍ、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 selected in the range of 1 to 30 μm, 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。この下塗り層の好ましい膜厚は５〜１０００ｎｍ以下、特に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 preferred thickness of the undercoat layer is 5 to 1000 nm or less, particularly 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。例えば次のようのな方法により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. 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、およびその密着性を高め、色素増感型太陽電池を作成した際に、長期間太陽光に暴露しても光発電効率を高く維持できる、色素増感型太陽電池用積層フィルムおよび電極を得ることができる。 According to the present invention, the processability of the porous semiconductor layer, and its adhesion, can be increased, and when producing a dye-sensitized solar cell, the photovoltaic efficiency can be maintained high even when exposed to sunlight for a long time. A laminated film and an electrode for a dye-sensitized solar cell can be obtained.
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した。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）光線透過率
（株）島津製作所製分光光度計ＭＰＣ３１００を用い、波長３７０ｎｍおよび４００ｎｍの光線透過率を測定した。
（４）ヘーズ値
ＪＩＳ Ｋ６７１４−１９５８に準じて、日本電色工業社製ヘーズ測定器（ＮＤＨ−２０）を使用して全光線透過率Ｔｔ（％）と散乱光線透過率Ｔｄ（％）とを測定し、以下の式よりヘーズ（％）を算出した。
ヘーズ値（％）＝（Ｔｄ／Ｔｔ）×１００
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. did. The average value of the film thicknesses of the obtained 300 locations was calculated and used as the film thickness.
(3) Light transmittance The light transmittance at wavelengths of 370 nm and 400 nm was measured using a spectrophotometer MPC3100 manufactured by Shimadzu Corporation.
(4) Haze value In accordance with JIS K6714-1958, the total light transmittance Tt (%) and the scattered light transmittance Td (%) were measured using a haze measuring device (NDH-20) manufactured by Nippon Denshoku Industries Co., Ltd. The haze (%) was calculated from the following formula.
Haze value (%) = (Td / Tt) × 100
（５）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
（６）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。
（７）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。
(5) Thermal contraction rate The film was held in an oven set at a temperature of 200 ° C. for 10 minutes without tension, 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 (6) Thickness of coating layer A small piece of film is embedded in epoxy resin (Epomount manufactured by Refine Tech Co., Ltd.) The embedded resin was sliced to a thickness of 50 nm using a Reichert-Jung Microtome2050, and observed with a transmission electron microscope (LEM-2000) at an acceleration voltage of 100 KV and a magnification of 100,000 times. It was measured.
(7) 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.
（８）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。
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。
(8) Surface tension Contact angle: θw, θy of water having a known surface tension and water-containing methylene to the transparent conductive thin film 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.
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.
（９）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。
（１０）Ｉ−Ｖ特性（光電流−電圧特性）
２５ｍｍ２大の色素増感型太陽電池を形成し、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。
（１１）耐侯促進試験
サンシャインウェザーメーター（スガ試験機（株）性、ＷＥＬ−ＳＵＮ−ＨＣＬ型）を使用し、ＪＩＳ−Ｋ−６７８３に準じて、１０００時間照射することにより曝露促進試験を行った。
(9) 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 ×.
(10) 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.
(11) Wrinkle resistance acceleration test Using a sunshine weather meter (Suga Test Instruments Co., Ltd., WEL-SUN-HCL type), an exposure acceleration test was conducted by irradiating for 1000 hours according to JIS-K-6783. .
[実施例１]
＜ポリエステルフィルムの作成＞
下記式（Ａ）に示す紫外線吸収剤を１重量％含有するポリエチレンテレフタレート（固有粘度：０．６５）を２０℃に維持した回転冷却ドラム上に溶融押出しして未延伸フィルムとした。
[Example 1]
<Creation of polyester film>
Polyethylene terephthalate (inherent viscosity: 0.65) containing 1% by weight of an ultraviolet absorber represented by the following formula (A) was melt-extruded on a rotating cooling drum maintained at 20 ° C. to obtain an unstretched film.
次いで縦方向に１００℃で３．４倍に延伸した後、その両面に下記の塗剤Ａをロールコーターで均一に塗布した。
次いで、この塗布フィルムを引き続いて９５℃で乾燥し、横方向に１２０℃で３．７倍に延伸し、２２０℃で幅方向に３％収縮させ熱固定し、厚さ１２５μｍのポリエステルフィルムを得た。なお、塗膜の厚さは０．０８μｍであった。
フィルムの波長３７０ｎｍでの光線透過率は０．５％、４００ｎｍでの光線透過率は８３．９％であった。
Next, the film was stretched 3.4 times in the longitudinal direction at 100 ° C., and then the following coating agent A was uniformly applied on both sides thereof with a roll coater.
Next, this coated film was subsequently dried at 95 ° C., stretched 3.7 times in the transverse direction at 120 ° C., and thermally fixed by shrinking 3% in the width direction at 220 ° C. to obtain a polyester film having a thickness of 125 μm. It was. The thickness of the coating film was 0.08 μm.
The light transmittance at a wavelength of 370 nm of the film was 0.5%, and the light transmittance at 400 nm was 83.9%.
＜塗剤Ａ＞
２，６−ナフタレンジカルボン酸ジメチル４８部、イソフタル酸ジメチル１４部、５−ナトリウムスルホイソフタル酸ジメチル４部、エチレングリコール３１部、ジエチレングリコール２部を反応器に仕込み、これにテトラブトキシチタン０．０５部を添加して窒素雰囲気下で温度を２３０℃にコントロールして加熱し、生成するメタノールを留去させてエステル交換反応を行った。次いで反応系の温度を徐々に２５５℃まで上昇させ系内を１ｍｍＨｇの減圧にして重縮合反応を行い、ポリエステルを得た。このポリエステル２５部をテトラヒドロフラン７５部に溶解させ、得られた溶液に１００００回転／分の高速攪拌下で水７５部を滴下して乳白色の分散体を得、次いでこの分散体を２０ｍｍＨｇの減圧下で蒸留し、テトラヒドロフランを留去し、固形分が２５重量％のポリエステルの水分散体を得た。
<Coating agent A>
48 parts of dimethyl 2,6-naphthalenedicarboxylate, 14 parts of dimethyl isophthalate, 4 parts of dimethyl 5-sodiumsulfoisophthalate, 31 parts of ethylene glycol and 2 parts of diethylene glycol are charged into a reactor, and 0.05 part of tetrabutoxy titanium Was added and heated under a nitrogen atmosphere while controlling the temperature at 230 ° C., and the produced methanol was distilled off to conduct a transesterification reaction. Subsequently, the temperature of the reaction system was gradually raised to 255 ° C., and the pressure inside the system was reduced to 1 mmHg to carry out a polycondensation reaction to obtain a polyester. 25 parts of this polyester was dissolved in 75 parts of tetrahydrofuran, and 75 parts of water was dropped into the resulting solution under high-speed stirring at 10,000 rpm to obtain a milky white dispersion. Then, this dispersion was subjected to a reduced pressure of 20 mmHg. Distillation was performed, and tetrahydrofuran was distilled off to obtain an aqueous dispersion of polyester having a solid content of 25% by weight.
次に、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。 Next, 3 parts of sodium lauryl sulfonate as a surfactant and 181 parts of ion-exchanged water are charged into a four-necked flask and the temperature is raised to 60 ° C. in a nitrogen stream, and then 0.5% ammonium persulfate is used as a polymerization initiator. Part, 0.2 part of sodium hydrogen nitrite is added, and further monomers 30.1 parts of methyl methacrylate, 21.9 parts of 2-isopropenyl-2-oxazoline, polyethylene oxide (n = 10) methacrylic acid A mixture of 39.4 parts and 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。 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.
上記のポリエステルの水分散体１０重量部、アクリルの水分散体５重量部と水溶液８５重量部を混合して、塗剤Ａを作成した。 Coating agent A was prepared by mixing 10 parts by weight of the above polyester aqueous dispersion, 5 parts by weight of the acrylic water dispersion and 85 parts by weight of the 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１５Ω／□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 15Ω / □.
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１６Ω／□、表面張力は７０．５ｍＮ／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 16Ω / □, and the surface tension was 70.5 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８０ｎｍで屈折率１．７５のＴｉＯＸ層、その上に厚さ７０ｎｍで屈折率２．１のＴｉＯ2層、更にその上に厚さ９５ｎｍで屈折率１．４５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５×１０-４Ｔｏｒｒ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>
On the surface opposite to the surface on which the transparent conductive layer of the laminated film is formed, a TiO X layer having a thickness of 80 nm and a refractive index of 1.75, a TiO 2 layer having a thickness of 70 nm and a refractive index of 2.1, and On top of that, SiO 2 having a thickness of 95 nm and a refractive index of 1.45 was formed by a high frequency sputtering method to form an antireflection treatment layer. When forming each electrostatic thin film, the degree of vacuum was 5 × 10 −4 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１６０℃で３０分間の熱処理を行って厚み４μｍ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) is applied with a bar coater and heat-treated at 160 ° C. for 30 minutes in the atmosphere. And a porous titanium dioxide layer was formed to a thickness of 4 μm to prepare an electrode of a dye-sensitized solar cell. 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、０.６８Ｖ、５．８ｍＡ／ｃｍ２、０．６９であり、その結果、光発電効率は２.７％であった。 As a result of performing IV measurement (effective area 25 mm 2 ) of the completed dye-sensitized solar cell, the open circuit voltage, short circuit current density, and fill factor were 0.68 V, 5.8 mA / cm 2 , and 0.69, respectively. As a result, the photovoltaic power generation efficiency was 2.7%.
次に耐侯性試験を行い、Ｉ−Ｖ測定を行った。開放電圧、短絡電流密度、曲線因子はそれぞれ、０.６９Ｖ、５．２ｍＡ／ｃｍ２、０．６７であり、その結果、光発電効率は２.４％であり、光発電効率の低下は非常に小さいものであった。 Next, a weather resistance test was performed and IV measurement was performed. The open circuit voltage, short circuit current density, and fill factor are 0.69 V, 5.2 mA / cm 2 , and 0.67, respectively. As a result, the photovoltaic power generation efficiency is 2.4%, and the photovoltaic power generation efficiency is greatly reduced. It was small.
[実施例２]
下記式（Ｂ）に示す紫外線吸収剤を２重量％含有するポリエチレンナフタレンジカルボキシレート（固有粘度：０．６１）を６０℃に維持した回転冷却ドラム上に溶融押出しして未延伸フィルムとした。
[Example 2]
Polyethylene naphthalene dicarboxylate (inherent viscosity: 0.61) containing 2% by weight of an ultraviolet absorber represented by the following formula (B) was melt extruded onto a rotating cooling drum maintained at 60 ° C. to obtain an unstretched film.
次いで縦方向に１４０℃で３．３倍に延伸した後、その両面に前記の塗剤Ａをロールコーターで均一に塗布した。
次いで、この塗布フィルムを引き続いて１２０℃で乾燥し、横方向に１４５℃で３．５倍に延伸し、２４０℃で幅方向に２％収縮させ熱固定し、厚さ１００μｍのポリエステルフィルムを得た。なお、塗膜の厚さは０．０８μｍであった。
フィルムの波長３７０ｎｍでの光線透過率は０．５％、４００ｎｍでの光線透過率は８３．９％であった。
Subsequently, after extending | stretching 3.3 times at 140 degreeC to the vertical direction, the said coating agent A was apply | coated uniformly with the roll coater on both surfaces.
Subsequently, this coated film was subsequently dried at 120 ° C., stretched 3.5 times at 145 ° C. in the transverse direction, and heat-fixed by shrinking 2% in the width direction at 240 ° C. to obtain a 100 μm thick polyester film. It was. The thickness of the coating film was 0.08 μm.
The light transmittance at a wavelength of 370 nm of the film was 0.5%, and the light transmittance at 400 nm was 83.9%.
実施例１と同様に、ハードコート層、透明導電層を設けた。透明導電層表面の表面抵抗値は１８Ω／□であった。次いで実施例１で用いた常圧プラズマ表面処理装置を用いて、酸素５％、窒素９５％の混合気体気流下（６０Ｌ／分）、１ｍ／分の速度で、透明導電層表面にプラズマ処理を行った。このとき、表面抵抗値は１８Ω／□、表面張力は６６．２ｍＮ／ｍであった。 Similarly to Example 1, a hard coat layer and a transparent conductive layer were provided. The surface resistance value of the transparent conductive layer surface was 18Ω / □. Next, using the atmospheric pressure plasma surface treatment apparatus used in Example 1, plasma treatment was performed on the surface of the transparent conductive layer at a rate of 1 m / min in a mixed gas stream of oxygen 5% and nitrogen 95% (60 L / min). went. At this time, the surface resistance value was 18Ω / □, and the surface tension was 66.2 mN / m.
更に実施例１と同様に、反射防止層、多孔質半導体層を形成し、電極を作成した。多孔質半導体層の密着性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。
この電極を用いて、実施例１と同様に色素増感型太陽電池を作成し、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、０.６５Ｖ、５．４ｍＡ／ｃｍ２、０．７０であり、その結果、光発電効率は２.５％であった。
Further, in the same manner as in Example 1, an antireflection layer and a porous semiconductor layer were formed to produce an electrode. When the adhesion evaluation of the porous semiconductor layer was performed, no peeling was observed, and the evaluation was good.
Using this electrode, a dye-sensitized solar cell was prepared in the same manner as in Example 1 and subjected to IV measurement (effective area 25 mm 2 ). As a result, the open circuit voltage, short-circuit current density, and fill factor were 0. 0.65 V, 5.4 mA / cm 2 , and 0.70. As a result, the photovoltaic generation efficiency was 2.5%.
次に耐侯性試験を行い、Ｉ−Ｖ測定を行った。開放電圧、短絡電流密度、曲線因子はそれぞれ、０.６４Ｖ、５．２ｍＡ／ｃｍ２、０．６９であり、その結果、光発電効率は２.３％であり、光発電効率の低下は非常に小さいものであった。 Next, a weather resistance test was performed and IV measurement was performed. The open circuit voltage, short circuit current density, and fill factor are 0.64 V, 5.2 mA / cm 2 , and 0.69, respectively. It was small.
[実施例３]
ポリエチレンテレフタレートに含有させる紫外線吸収剤を下記式（Ｃ）に示す化合物に変更する他は、実施例１と同様にポリエステルフィルムを作成した。
[Example 3]
A polyester film was prepared in the same manner as in Example 1 except that the ultraviolet absorber contained in polyethylene terephthalate was changed to the compound represented by the following formula (C).
フィルムの波長３７０ｎｍでの光線透過率は０．３％、４００ｎｍでの光線透過率は８１．２％であった。 The film had a light transmittance of 0.3% at a wavelength of 370 nm and a light transmittance of 81.2% at 400 nm.
実施例１と同様に、ハードコート層、透明導電層を設けた。透明導電層表面の表面抵抗値は２０Ω／□であった。次いで実施例１で用いた常圧プラズマ表面処理装置を用いて、酸素３０％、窒素７０％の混合気体気流下（６０Ｌ／分）、１ｍ／分の速度で、透明導電層表面にプラズマ処理を行った。このとき、表面抵抗値は２１Ω／□、表面張力は４３．２ｍＮ／ｍであった。 Similarly to Example 1, a hard coat layer and a transparent conductive layer were provided. The surface resistance value of the transparent conductive layer surface was 20Ω / □. Next, using the atmospheric pressure plasma surface treatment apparatus used in Example 1, plasma treatment was performed on the surface of the transparent conductive layer at a rate of 1 m / min in a mixed gas stream of oxygen 30% and nitrogen 70% (60 L / min). went. At this time, the surface resistance value was 21Ω / □, and the surface tension was 43.2 mN / m.
更に実施例１と同様に、反射防止層、多孔質半導体層を形成し、電極を作成した。多孔質半導体層の密着性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。
この電極を用いて、実施例１と同様に色素増感型太陽電池を作成し、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、０.６６Ｖ、５．０ｍＡ／ｃｍ２、０．６５であり、その結果、光発電効率は２.１％であった。
Further, in the same manner as in Example 1, an antireflection layer and a porous semiconductor layer were formed to produce an electrode. When the adhesion evaluation of the porous semiconductor layer was performed, no peeling was observed, and the evaluation was good.
Using this electrode, a dye-sensitized solar cell was prepared in the same manner as in Example 1 and subjected to IV measurement (effective area 25 mm 2 ). As a result, the open circuit voltage, short-circuit current density, and fill factor were 0. 0.66 V, 5.0 mA / cm 2 , 0.65, and as a result, the photovoltaic efficiency was 2.1%.
次に耐侯性試験を行い、Ｉ−Ｖ測定を行った。開放電圧、短絡電流密度、曲線因子はそれぞれ、０.６６Ｖ、４．７ｍＡ／ｃｍ２、０．６３であり、その結果、光発電効率は２.０％であり、光発電効率の低下は非常に小さいものであった。 Next, a weather resistance test was performed and IV measurement was performed. The open circuit voltage, short circuit current density, and fill factor are 0.66 V, 4.7 mA / cm 2 , and 0.63, respectively. It was small.
[比較例１]
ポリエチレンテレフタレートに紫外線吸収剤を入れない他は、実施例１と同様に色素増感型太陽電池用電極を作成した。なお、ポリエステルフィルムの波長３７０ｎｍでの光線透過率は８４．６％、４００ｎｍでの光線透過率は８７．７％であった。この電極を用いて実施例１と同様に色素増感型太陽電池を作成し、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、０.６９Ｖ、６．２ｍＡ／ｃｍ２、０．６８であり、その結果、光発電効率は２.９％であった。
[Comparative Example 1]
A dye-sensitized solar cell electrode was prepared in the same manner as in Example 1 except that no ultraviolet absorber was added to polyethylene terephthalate. The light transmittance of the polyester film at a wavelength of 370 nm was 84.6%, and the light transmittance at 400 nm was 87.7%. Using this electrode, a dye-sensitized solar cell was prepared in the same manner as in Example 1 and subjected to IV measurement (effective area 25 mm 2 ). As a result, the open-circuit voltage, short-circuit current density, and fill factor were 0. It was 69 V, 6.2 mA / cm 2 , 0.68, and as a result, the photovoltaic generation efficiency was 2.9%.
次に耐侯性試験を行い、Ｉ−Ｖ測定を行った。開放電圧、短絡電流密度、曲線因子はそれぞれ、０.６３Ｖ、２．２ｍＡ／ｃｍ２、０．５８であり、その結果、光発電効率は０.８％であり、光発電効率の低下が顕著であった。 Next, a weather resistance test was performed and IV measurement was performed. The open circuit voltage, short circuit current density, and fill factor are 0.63 V, 2.2 mA / cm 2 , and 0.58, respectively. As a result, the photovoltaic efficiency is 0.8%, and the photovoltaic efficiency is significantly reduced. Met.
[比較例２]
ポリエチレンテレフタレートに含有させる紫外線吸収剤を６重量％とする他は、実施例１と同様に色素増感型太陽電池用電極を作成した。なお、ポリエステルフィルムの波長３７０ｎｍでの光線透過率は０．１％、４００ｎｍでの光線透過率は６６．２％であった。この電極を用いて実施例１と同様に色素増感型太陽電池を作成し、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、０.６２Ｖ、４．１ｍＡ／ｃｍ２、０．６４であり、その結果、光発電効率は１．６％と低いものであった。
[Comparative Example 2]
A dye-sensitized solar cell electrode was prepared in the same manner as in Example 1 except that the ultraviolet absorber contained in polyethylene terephthalate was 6% by weight. The light transmittance of the polyester film at a wavelength of 370 nm was 0.1%, and the light transmittance at 400 nm was 66.2%. Using this electrode, a dye-sensitized solar cell was prepared in the same manner as in Example 1 and subjected to IV measurement (effective area 25 mm 2 ). As a result, the open-circuit voltage, short-circuit current density, and fill factor were 0. 62V, 4.1 mA / cm 2 , 0.64. As a result, the photovoltaic generation efficiency was as low as 1.6%.
[比較例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５０％：５０％とし、積層フィルムを作成した。プラズマ処理後の表面張力は３７．８ｍＮ／ｍであった。この積層フィルムに、実施例１同様、多孔質半導体層を形成して電極を作成した。多孔質半導体層の密着性評価を行ったところ、部分的に剥離が観察され、評価は△であった。
[Comparative Example 3]
In Example 1, the ratio of nitrogen and oxygen in the gas used when performing the plasma treatment was 50%: 50%, and a laminated film was prepared. The surface tension after the plasma treatment was 37.8 mN / m. As in Example 1, an electrode was formed by forming a porous semiconductor layer on this laminated film. When the adhesion evaluation of the porous semiconductor layer was performed, peeling was partially observed, and the evaluation was Δ.
この電極を用いて実施例１と同様に色素増感型太陽電池を作成し、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、０.５８Ｖ、４．２ｍＡ／ｃｍ２、０．５９であり、その結果、光発電効率は１．４％と低いものであった。 Using this electrode, a dye-sensitized solar cell was prepared in the same manner as in Example 1 and subjected to IV measurement (effective area 25 mm 2 ). As a result, the open-circuit voltage, short-circuit current density, and fill factor were 0. 58 V, 4.2 mA / cm 2 , 0.59. As a result, the photovoltaic power generation efficiency was as low as 1.4%.
Claims (9)
で表わされる環状イミノエステル及び下記式（II）
下記式（II）-ｂ
で表わされる環状イミノエステルから選ばれる少なくとも１種の化合物であるである請求項４記載の色素増感型太陽電池用積層フィルム。 The ultraviolet absorber is represented by the following formula (I)
And a cyclic imino ester represented by the following formula (II)
The laminated film for a dye-sensitized solar cell according to claim 4, which is at least one compound selected from cyclic iminoesters represented by:
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| EP1808928B1 (en) * | 2004-10-13 | 2010-12-15 | Teijin Dupont Films Japan Limited | Multilayer body for dye-sensitized solar cell, electrode for dye-sensitized solar cell and method for producing same |
| JP4944419B2 (en) * | 2005-10-04 | 2012-05-30 | 帝人デュポンフィルム株式会社 | Biaxially oriented polyester film for solid polymer electrolyte membrane reinforcement |
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| JP5348986B2 (en) * | 2008-09-25 | 2013-11-20 | 富士フイルム株式会社 | Conductive material and manufacturing method thereof |
| JP5581831B2 (en) * | 2009-06-18 | 2014-09-03 | 東洋紡株式会社 | Polyester film for solar cell and method for producing the same |
| JP5303013B2 (en) * | 2011-08-22 | 2013-10-02 | 三菱樹脂株式会社 | Polyester film for dye-sensitized solar cells |
| JP6118676B2 (en) * | 2013-07-26 | 2017-04-19 | 三菱樹脂株式会社 | Transparent conductive film |
| KR102161963B1 (en) * | 2013-02-06 | 2020-10-06 | 미쯔비시 케미컬 주식회사 | Transparent stacked film, transparent conductive film, and gas barrier stacked film |
| JP6469948B2 (en) * | 2013-08-22 | 2019-02-13 | 帝人フィルムソリューション株式会社 | Transparent electrode film |
| KR101541646B1 (en) * | 2014-03-28 | 2015-08-04 | 한국에너지기술연구원 | Dye-sensitive solar cell with ultraviolet- absorptiveness |
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2004
- 2004-03-03 JP JP2004058734A patent/JP4456894B2/en not_active Expired - Lifetime
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