JP2012234959A - Photovoltaic thread covered with thermoplastic resin, and method for manufacturing the same - Google Patents

Photovoltaic thread covered with thermoplastic resin, and method for manufacturing the same Download PDF

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JP2012234959A
JP2012234959A JP2011102297A JP2011102297A JP2012234959A JP 2012234959 A JP2012234959 A JP 2012234959A JP 2011102297 A JP2011102297 A JP 2011102297A JP 2011102297 A JP2011102297 A JP 2011102297A JP 2012234959 A JP2012234959 A JP 2012234959A
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thermoplastic resin
layer
yarn
photovoltaic
resin layer
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Shuichi Motonaka
修一 源中
Yuko Fukaki
裕子 深城
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Suminoe Textile Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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
    • Y02E10/549—Organic PV cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

PROBLEM TO BE SOLVED: To provide a photovoltaic thread achieving excellent durability, flexibility, and high efficiency in power generation performance.SOLUTION: A photovoltaic thread excellent in durability comprises a conductive thread successively covered with an active layer, a conductive polymer layer, and a thermoplastic resin layer from the center side therearound, the thickness of the thermoplastic resin layer is in the range of 0.1 to 50 μm, and the ratio of the thickness of the thermoplastic resin layer to the diameter of the conductive thread is in the range of 1/20 to 1/5. A method for manufacturing the photovoltaic thread is also provided.

Description

本発明は、優れた耐熱変形性と耐摩擦性のある光発電糸及びその製造方法に関する。   The present invention relates to a photovoltaic yarn having excellent heat distortion resistance and friction resistance and a method for producing the same.

地球温暖化をもたらす化石燃料の代替エネルギーとして、つまり、温室効果ガス排出量を削減した低炭素社会の実現に不可欠なエネルギーとして、太陽光エネルギーを直接電力に変換する太陽電池を利用した太陽光発電の普及が期待されている。   Solar power generation using solar cells that directly convert solar energy into electric power as an alternative energy to fossil fuels that cause global warming, that is, as an indispensable energy for realizing a low-carbon society that reduces greenhouse gas emissions Is expected to spread.

太陽電池は、光起電力効果により太陽光を即時に電力に変換するもので、従来シリコン太陽電池が主流であった。近年、製法が簡便で生産コストを低く抑えることのできる有機化合物を用いた太陽電池の開発が行われている。有機化合物を用いた太陽電池には、色素増感太陽電池、有機薄膜太陽電池がある。   Solar cells convert solar light into electric power instantly due to the photovoltaic effect, and conventional silicon solar cells have been the mainstream. In recent years, solar cells have been developed using organic compounds that are simple in production and can keep production costs low. Solar cells using organic compounds include dye-sensitized solar cells and organic thin-film solar cells.

このような有機化合物を用いた太陽電池としては、特許文献１には透明材料の管の内面に透明導電層、色素増感多孔質半導体層、電解質層を順に設け、管の中央部分に対極が挿入された構造の色素増感光電変換素子が開示されている。   As a solar cell using such an organic compound, in Patent Document 1, a transparent conductive layer, a dye-sensitized porous semiconductor layer, and an electrolyte layer are sequentially provided on the inner surface of a transparent material tube, and a counter electrode is provided at the central portion of the tube. A dye-sensitized photoelectric conversion element having an inserted structure is disclosed.

しかしながら、特許文献１の技術は、布帛にするための製編あるいは製織に好適とはいえなかった。
特開２００７−０１２５４５ However, the technique of Patent Document 1 is not suitable for knitting or weaving to make a fabric.
JP2007-012545

この発明は、かかる技術的背景に鑑みてなされたものであって、耐久性に優れると共に、柔軟で高効率な発電性能を発揮する光発電糸を提供する。   The present invention has been made in view of such a technical background, and provides a photovoltaic yarn that is excellent in durability and that exhibits flexible and highly efficient power generation performance.

本発明者は、このような課題を解決するために鋭意検討の結果、導電糸の周囲に中心側から順に、活性層、導電性高分子層及び熱可塑性樹脂層が積層された光発電糸において、該熱可塑性樹脂層の厚さが０．１μｍ〜５０μｍ、かつ、該熱可塑性樹脂層の厚さが前記導電糸の直径に対して１／２０〜１／５である耐久性に優れた光発電糸を見出し本発明に到達した。本発明は以下の手段を提供する。   As a result of intensive studies to solve such problems, the present inventor has obtained a photovoltaic yarn in which an active layer, a conductive polymer layer, and a thermoplastic resin layer are laminated in order from the center side around the conductive yarn. The light having excellent durability in which the thickness of the thermoplastic resin layer is 0.1 μm to 50 μm, and the thickness of the thermoplastic resin layer is 1/20 to 1/5 with respect to the diameter of the conductive yarn. The power generation yarn has been found and the present invention has been reached. The present invention provides the following means.

［１］導電糸の周囲に中心側から順に、活性層、導電性高分子層及び熱可塑性樹脂層が積層された光発電糸において、該熱可塑性樹脂層の厚さが０．１μｍ〜５０μｍ、かつ、該熱可塑性樹脂層の厚さが前記導電糸の直径に対して１／２０〜１／５であることを特徴とする光発電糸。   [1] In a photovoltaic yarn in which an active layer, a conductive polymer layer, and a thermoplastic resin layer are laminated in order from the center side around the conductive yarn, the thickness of the thermoplastic resin layer is 0.1 μm to 50 μm, And the thickness of this thermoplastic resin layer is 1 / 20-1 / 5 with respect to the diameter of the said conductive yarn, The photovoltaic yarn characterized by the above-mentioned.

［２］前記活性層が、ポリチオフェン誘導体及びフラーレン誘導体からなる前項１に記載の光発電糸。   [2] The photovoltaic yarn according to item 1 above, wherein the active layer is composed of a polythiophene derivative and a fullerene derivative.

［３］前記導電性高分子層が、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）／ポリスチレンスルホン酸（ＰＳＳ）、ポリアニリン（ＰＡＮＩ）／ポリスチレンスルホン酸（ＰＳＳ）から選ばれる１種である前項１または２に記載の光発電糸。   [3] The conductive polymer layer according to item 1 or 2, wherein the conductive polymer layer is one selected from polyethylene dioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS) and polyaniline (PANI) / polystyrene sulfonic acid (PSS). Photovoltaic yarn.

［４］前記熱可塑性樹脂層が、ＥＶＡ（エチレン−酢酸ビニル共重合樹脂）、ＰＶＢ（ポリビニルブチラール樹脂）から選ばれる１種である前項１〜３のいずれか１項に記載の光発電糸。   [4] The photovoltaic yarn according to any one of items 1 to 3, wherein the thermoplastic resin layer is one selected from EVA (ethylene-vinyl acetate copolymer resin) and PVB (polyvinyl butyral resin).

［５］酸素濃度１％以下の不活性ガス雰囲気下で、導電糸の周囲に活性層を塗工し乾燥することにより活性層を得る活性層積層工程と、前記活性層の周囲に導電性高分子層を塗工し乾燥することにより導電性高分子層を得る導電性高分子層積層工程と、前記導電性高分子層の周囲に熱可塑性樹脂層を塗工することにより該熱可塑性樹脂層の厚さが０．１μｍ〜５０μｍ、かつ、該熱可塑性樹脂層の厚さが前記導電糸の直径に対して１／２０〜１／５である熱可塑性樹脂層を得る熱可塑性樹脂層積層工程と、前記熱可塑性樹脂層に５０ｋＧｙ〜２５０ｋＧｙの範囲の電子線照射を行う電子線照射工程とを順に実施することを特徴とする光発電糸の製造方法。   [5] An active layer laminating step in which an active layer is obtained by applying and drying an active layer around a conductive yarn in an inert gas atmosphere with an oxygen concentration of 1% or less, and a conductive high layer around the active layer. A conductive polymer layer laminating step for obtaining a conductive polymer layer by coating and drying a molecular layer, and the thermoplastic resin layer by coating a thermoplastic resin layer around the conductive polymer layer Thermoplastic resin layer lamination step for obtaining a thermoplastic resin layer having a thickness of 0.1 μm to 50 μm and a thickness of the thermoplastic resin layer of 1/20 to 1/5 of the diameter of the conductive yarn And an electron beam irradiation step of sequentially irradiating the thermoplastic resin layer with an electron beam in the range of 50 kGy to 250 kGy.

［６］前記活性層積層工程において、前記活性層としてポリチオフェン誘導体及びフラーレン誘導体を用いる前項５に記載の光発電糸の製造方法。   [6] The method for producing a photovoltaic yarn according to item 5 above, wherein in the active layer laminating step, a polythiophene derivative and a fullerene derivative are used as the active layer.

［７］前記導電性高分子層積層工程において、前記導電性高分子層としてポリエチレンジオキシチオフェン（ＰＥＤＯＴ）／ポリスチレンスルホン酸（ＰＳＳ）、ポリアニリン（ＰＡＮＩ）／ポリスチレンスルホン酸（ＰＳＳ）から選ばれる１種を用いる前項５または６に記載の光発電糸の製造方法。   [7] In the conductive polymer layer laminating step, the conductive polymer layer is selected from polyethylene dioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS), polyaniline (PANI) / polystyrene sulfonic acid (PSS) 1 7. The method for producing a photovoltaic yarn according to item 5 or 6, wherein a seed is used.

［８］前記熱可塑性樹脂層積層工程において、前記熱可塑性樹脂としてＥＶＡ（エチレン−酢酸ビニル共重合樹脂）、ＰＶＢ（ポリビニルブチラール樹脂）から選ばれる１種を用いる前項５〜７のいずれか１項に記載の光発電糸の製造方法。   [8] Any one of items 5 to 7 above, in which one kind selected from EVA (ethylene-vinyl acetate copolymer resin) and PVB (polyvinyl butyral resin) is used as the thermoplastic resin in the thermoplastic resin layer laminating step. A method for producing a photovoltaic yarn according to claim 1.

［１］の発明では、導電糸の周囲に中心側から順に、活性層、導電性高分子層及び熱可塑性樹脂層が積層された光発電糸において、該熱可塑性樹脂層の厚さが０．１μｍ〜５０μｍ、かつ、該熱可塑性樹脂層の厚さが前記導電糸の直径に対して１／２０〜１／５であるので酸素及び水分を充分遮蔽すると共に、耐久性に優れた光発電糸とすることができる。   In the invention of [1], in the photovoltaic yarn in which the active layer, the conductive polymer layer, and the thermoplastic resin layer are sequentially laminated around the conductive yarn from the center side, the thickness of the thermoplastic resin layer is 0.00. 1 μm to 50 μm, and the thickness of the thermoplastic resin layer is 1/20 to 1/5 of the diameter of the conductive yarn, so that it sufficiently shields oxygen and moisture and has excellent durability. It can be.

［２］の発明では、前記活性層が、ポリチオフェン誘導体及びフラーレン誘導体からなり、電子供与性のポリチオフェン誘導体がドナー、電子吸引性の強いフラーレン誘導体がアクセプターとして働くので、太陽光の照射により光起電力が発生し、高効率な発電性能を発揮する光発電糸とすることができる。   In the invention of [2], the active layer is composed of a polythiophene derivative and a fullerene derivative, the electron donating polythiophene derivative serves as a donor, and the fullerene derivative having a strong electron withdrawing property serves as an acceptor. Is generated, and it can be set as a photovoltaic yarn that exhibits highly efficient power generation performance.

［３］の発明では、前記導電性高分子層が、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）／ポリスチレンスルホン酸（ＰＳＳ）、ポリアニリン（ＰＡＮＩ）／ポリスチレンスルホン酸（ＰＳＳ）であるので安定して活性層３で発生した正孔を取り出すことができる。   In the invention of [3], since the conductive polymer layer is polyethylenedioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS), polyaniline (PANI) / polystyrene sulfonic acid (PSS), the active layer 3 is stably provided. The holes generated in can be taken out.

［４］の発明では、前記熱可塑性樹脂層が、ＥＶＡ（エチレン−酢酸ビニル共重合樹脂）、ＰＶＢ（ポリビニルブチラール樹脂）から選ばれる１種であるので比較的容易に熱溶解し塗工することができる。さらに、酸素及び水分を遮蔽するので導電性高分子層及び活性層を保護すると共に、光発電糸に耐久性を付与することができる。   In the invention of [4], since the thermoplastic resin layer is one selected from EVA (ethylene-vinyl acetate copolymer resin) and PVB (polyvinyl butyral resin), it is relatively easily melted and coated. Can do. Furthermore, since oxygen and moisture are shielded, the conductive polymer layer and the active layer can be protected and durability can be imparted to the photovoltaic yarn.

［５］の発明では、活性層積層工程と、導電性高分子層積層工程と、熱可塑性樹脂層積層工程及び電子線照射工程を順に実施することによって、耐久性に優れた柔軟で高効率な発電性能を発揮する光発電糸を製造することができる。該熱可塑性樹脂層の厚さが０．１μｍ〜５０μｍ、かつ、該熱可塑性樹脂層の厚さが前記導電糸の直径に対して１／２０〜１／５であるので酸素及び水分を充分に遮蔽することができる。しかも、５０ｋＧｙ〜２５０ｋＧｙの範囲の電子線照射を実施するので熱可塑性樹脂層の架橋を促進するので耐久性を向上させることができる。活性層積層工程、導電性高分子層積層工程、熱可塑性樹脂層積層工程及び電子線照射工程を酸素濃度１％以下の不活性ガス雰囲気下で実施することで、活性層、導電性高分子層及び熱可塑性樹脂層における発電性能を損なう酸素を遮蔽することができる。さらに電子線照射工程では熱可塑性樹脂層の架橋反応を阻害するのを防止することができる。   In the invention of [5], by performing the active layer laminating step, the conductive polymer layer laminating step, the thermoplastic resin layer laminating step and the electron beam irradiation step in this order, it is flexible and highly efficient with excellent durability. It is possible to produce a photovoltaic yarn that exhibits power generation performance. Since the thickness of the thermoplastic resin layer is 0.1 μm to 50 μm and the thickness of the thermoplastic resin layer is 1/20 to 1/5 with respect to the diameter of the conductive yarn, oxygen and moisture are sufficiently absorbed. Can be shielded. And since electron beam irradiation of the range of 50 kGy-250 kGy is implemented, since bridge | crosslinking of a thermoplastic resin layer is accelerated | stimulated, durability can be improved. By carrying out the active layer lamination step, the conductive polymer layer lamination step, the thermoplastic resin layer lamination step and the electron beam irradiation step in an inert gas atmosphere having an oxygen concentration of 1% or less, the active layer, the conductive polymer layer In addition, oxygen that impairs power generation performance in the thermoplastic resin layer can be shielded. Further, it is possible to prevent the crosslinking reaction of the thermoplastic resin layer from being inhibited in the electron beam irradiation step.

［６］の発明では、前記活性層積層工程において、前記活性層としてポリチオフェン誘導体及びフラーレン誘導体を用いるので電子供与性のポリチオフェン誘導体がドナー、電子吸引性の強いフラーレン誘導体がアクセプターとして働くので、太陽光の照射により光起電力が発生し、高効率な光発電糸を製造することができる。   In the invention of [6], in the active layer laminating step, since a polythiophene derivative and a fullerene derivative are used as the active layer, an electron-donating polythiophene derivative serves as a donor, and a fullerene derivative having a strong electron-withdrawing property serves as an acceptor. Photovoltaic power is generated by irradiation of, and a highly efficient photovoltaic yarn can be manufactured.

［７］の発明では、前記導電性高分子層積層工程において、前記導電性高分子層としてポリエチレンジオキシチオフェン（ＰＥＤＯＴ）／ポリスチレンスルホン酸（ＰＳＳ）、ポリアニリン（ＰＡＮＩ）／ポリスチレンスルホン酸（ＰＳＳ）から選ばれる１種を用いるので安定して活性層３で発生した正孔を取り出すことができる光発電糸を製造することができる。   In the invention of [7], in the conductive polymer layer laminating step, polyethylenedioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS), polyaniline (PANI) / polystyrene sulfonic acid (PSS) is used as the conductive polymer layer. Thus, a photovoltaic yarn capable of stably extracting holes generated in the active layer 3 can be produced.

［８］の発明では、前記熱可塑性樹脂層積層工程において、前記熱可塑性樹脂としてＥＶＡ（エチレン−酢酸ビニル共重合樹脂）、ＰＶＢ（ポリビニルブチラール樹脂）から選ばれる１種を用いるので比較的容易に熱溶解し塗工することができる。さらに、酸素及び水分を遮蔽するので導電性高分子層及び活性層を保護すると共に、耐久性のある光発電糸を製造することができる。   In the invention of [8], in the thermoplastic resin layer laminating step, one kind selected from EVA (ethylene-vinyl acetate copolymer resin) and PVB (polyvinyl butyral resin) is used as the thermoplastic resin relatively easily. Can be melted and coated. Furthermore, since oxygen and moisture are shielded, the conductive polymer layer and the active layer can be protected, and a durable photovoltaic thread can be manufactured.

本発明に係る光発電糸の一実施形態を図１に示す。本実施形態の光発電糸は、導電糸の周囲に中心側から順に、活性層、導電性高分子層及び熱可塑性樹脂層が積層された光発電糸である。図において、１は光発電糸、２は導電糸、３は活性層、４は導電性高分子層、５は熱可塑性樹脂層を示している。光発電糸１は、導電糸２の周囲に活性層３を積層し、さらに導電性高分子層４を積層し、最後に熱可塑性樹脂層５を積層している。   One embodiment of the photovoltaic yarn according to the present invention is shown in FIG. The photovoltaic yarn of this embodiment is a photovoltaic yarn in which an active layer, a conductive polymer layer, and a thermoplastic resin layer are laminated in this order from the center side around the conductive yarn. In the figure, 1 is a photovoltaic yarn, 2 is a conductive yarn, 3 is an active layer, 4 is a conductive polymer layer, and 5 is a thermoplastic resin layer. In the photovoltaic yarn 1, an active layer 3 is laminated around a conductive yarn 2, a conductive polymer layer 4 is further laminated, and finally a thermoplastic resin layer 5 is laminated.

導電糸２としては、例えば天然繊維（綿等）又は合成繊維（ポリエステル繊維、ナイロン繊維等）の周りに金属（アルミニウム、ステンレス、金、銀等）薄膜を蒸着処理した繊維、無機繊維（ステンレス鋼繊維等）、導電性繊維（カーボン練り込み繊維、導電性高分子からなる繊維）を採用することができる。中でも軽量で柔軟性があるのでアルミニウムを蒸着するのが好ましい。導電糸２の繊度は、０．００３デシテックス〜１０２１０デシテックスの範囲が好ましい。０．００３デシテックスより細い繊度では、発電糸の強度が弱くなり、取扱いが困難となるので好ましくない。また、１０２１０デシテックスより太い繊度では、発電糸の柔軟性が不充分となるので好ましくない。   Examples of the conductive yarn 2 include fibers obtained by vapor-depositing a metal (aluminum, stainless steel, gold, silver, etc.) thin film around natural fibers (cotton, etc.) or synthetic fibers (polyester fibers, nylon fibers, etc.), inorganic fibers (stainless steel). Fibers), conductive fibers (carbon kneaded fibers, conductive polymer fibers) can be used. Of these, aluminum is preferably deposited because of its light weight and flexibility. The fineness of the conductive yarn 2 is preferably in the range of 0.003 dtex to 10210 dtex. Fineness finer than 0.003 dtex is not preferable because the strength of the power generation yarn becomes weak and handling becomes difficult. A fineness greater than 10210 dtex is not preferable because the flexibility of the power generation yarn becomes insufficient.

活性層３としては、ポリチオフェン誘導体及びフラーレン誘導体からなり、電子供与性のポリチオフェン誘導体がドナー、電子吸引性の強いフラーレン誘導体がアクセプターとして働くので、太陽光の照射により光起電力が発生し、高効率な光発電糸とすることができる。ポリチオフェン誘導体としては、ポリ−３−ヘキシルチオフェン（Ｐ３ＨＴ）、ポリ−３−オクチルチオフェン（Ｐ３ＯＴ）、ポリ−３−ドデシルチオフェン（Ｐ３ＤＤＴ）を挙げることができる。中でも、高い開放電圧を与えるポリ−３−ヘキシルチオフェン（Ｐ３ＨＴ）が好ましい。また、フラーレン誘導体としては、フラーレン骨格を有するものであれば特に限定されないが、例えば、フェニルＣ６１ブチル酸メチルエステル（ＰＣＢＭ）を挙げることができる。 The active layer 3 is composed of a polythiophene derivative and a fullerene derivative. The electron donating polythiophene derivative serves as a donor, and the fullerene derivative having a strong electron withdrawing property serves as an acceptor. It can be made into a photovoltaic power generation yarn. Examples of the polythiophene derivative include poly-3-hexylthiophene (P3HT), poly-3-octylthiophene (P3OT), and poly-3-dodecylthiophene (P3DDT). Among these, poly-3-hexylthiophene (P3HT) that gives a high open-circuit voltage is preferable. The fullerene derivative is not particularly limited as long as it has a fullerene skeleton, and examples thereof include phenyl C 61 butyric acid methyl ester (PCBM).

導電性高分子層４としては、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）／ポリスチレンスルホン酸（ＰＳＳ）、ポリアニリン（ＰＡＮＩ）／ポリスチレンスルホン酸ＰＳＳから選ばれる１種を採用することができる。ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）にポリスチレンスルホン酸（ＰＳＳ）がドープされた混合物、及びポリアニリン（ＰＡＮＩ）にポリスチレンスルホン酸（ＰＳＳ）がドープされた混合物は活性層３で発生した正孔を安定的に取り出すので、高効率な光発電糸とすることができる。   As the conductive polymer layer 4, one selected from polyethylene dioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS) and polyaniline (PANI) / polystyrene sulfonic acid PSS can be employed. A mixture of polyethylene dioxythiophene (PEDOT) doped with polystyrene sulfonic acid (PSS) and a mixture of polyaniline (PANI) doped with polystyrene sulfonic acid (PSS) can stably generate holes generated in the active layer 3. Since it is taken out, a highly efficient photovoltaic yarn can be obtained.

熱可塑性樹脂層５としては、熱可塑性樹脂としてＥＶＡ（エチレン−酢酸ビニル共重合樹脂）、ＰＶＢ（ポリビニルブチラール樹脂）から選ばれる１種を採用するので比較的容易に熱溶解し塗工することができる。さらに、酸素及び水分を遮蔽するので導電性高分子層４及び活性層３を保護すると共に、耐久性のある光発電糸１を製造することができる。   As the thermoplastic resin layer 5, one kind selected from EVA (ethylene-vinyl acetate copolymer resin) and PVB (polyvinyl butyral resin) is adopted as the thermoplastic resin, so that it can be melted and coated relatively easily. it can. Furthermore, since the oxygen and moisture are shielded, the conductive polymer layer 4 and the active layer 3 can be protected, and a durable photovoltaic yarn 1 can be manufactured.

本発明に係る光発電糸１の製造方法は、導電糸２の周囲に中心側から順に、活性層３、導電性高分子層４及び熱可塑性樹脂層５が積層された光発電糸１の製造方法において、酸素濃度１％以下の不活性ガス雰囲気下で、導電糸２の周囲に活性層３を塗工し乾燥することにより活性層３を得る活性層積層工程と、前記活性層３の周囲に導電性高分子層４を塗工し乾燥することにより導電性高分子層４を得る導電性高分子層積層工程と、前記導電性高分子層４の周囲に熱可塑性樹脂層５を塗工することにより該熱可塑性樹脂層５の厚さが０．１μｍ〜５０μｍ、かつ、該熱可塑性樹脂層５の厚さが前記導電糸２の直径に対して１／２０〜１／５である熱可塑性樹脂層５を得る熱可塑性樹脂層積層工程と、前記熱可塑性樹脂層５に５０ｋＧｙ〜２５０ｋＧｙの範囲の電子線照射を行う電子線照射工程とを順に実施することを特徴とする。   The manufacturing method of the photovoltaic yarn 1 according to the present invention is the manufacturing of the photovoltaic yarn 1 in which the active layer 3, the conductive polymer layer 4, and the thermoplastic resin layer 5 are laminated in this order from the center side around the conductive yarn 2. In the method, an active layer laminating step of obtaining an active layer 3 by applying and drying the active layer 3 around the conductive yarn 2 in an inert gas atmosphere having an oxygen concentration of 1% or less, and a surrounding of the active layer 3 The conductive polymer layer 4 is coated and dried to obtain the conductive polymer layer 4 and the thermoplastic polymer layer 5 is applied around the conductive polymer layer 4. By doing so, the thickness of the thermoplastic resin layer 5 is 0.1 μm to 50 μm, and the thickness of the thermoplastic resin layer 5 is 1/20 to 1/5 with respect to the diameter of the conductive yarn 2. The thermoplastic resin layer lamination step for obtaining the plastic resin layer 5, and 50 kGy to 250 k in the thermoplastic resin layer 5 An electron beam irradiation step of performing electron beam irradiation in the range of kGy is performed in order.

本発明に係る光発電糸１の製造方法によれば、活性層積層工程と、導電性高分子層積層工程と、熱可塑性樹脂層積層工程及び電子線照射工程を順に実施することによって、耐久性に優れた柔軟で高効率な発電性能を発揮する光発電糸１を製造することができる。該熱可塑性樹脂層５の厚さが０．１μｍ〜５０μｍ、かつ、該熱可塑性樹脂層５の厚さが前記導電糸２の直径に対して１／２０〜１／５であるので酸素及び水分を充分遮蔽すると共に、耐久性に優れた光発電糸１とすることができ、しかも、５０ｋＧｙ〜２５０ｋＧｙの範囲の電子線照射を実施するので熱可塑性樹脂層５の架橋を促進するため耐久性の向上した光発電糸１を製造することができる。活性層積層工程、導電性高分子層積層工程、熱可塑性樹脂層積層工程及び電子線照射工程を酸素濃度１％以下の不活性ガス雰囲気下で実施することで、活性層３、導電性高分子層４及び熱可塑性樹脂層５における発電性能を損なう酸素を遮蔽することができる。さらに電子線照射工程では熱可塑性樹脂層５の架橋反応を阻害するのを防止することができるので、耐久性に優れた光発電糸１を製造することができる。   According to the method for producing the photovoltaic yarn 1 according to the present invention, the active layer laminating step, the conductive polymer layer laminating step, the thermoplastic resin layer laminating step, and the electron beam irradiation step are performed in this order, thereby improving durability. It is possible to produce a photovoltaic yarn 1 that exhibits excellent and flexible and highly efficient power generation performance. Since the thickness of the thermoplastic resin layer 5 is 0.1 μm to 50 μm and the thickness of the thermoplastic resin layer 5 is 1/20 to 1/5 with respect to the diameter of the conductive yarn 2, oxygen and moisture Is sufficiently durable and can be made into a photovoltaic yarn 1 having excellent durability, and further, since the electron beam irradiation in the range of 50 kGy to 250 kGy is performed, the crosslinking of the thermoplastic resin layer 5 is promoted, so that the durability is high. An improved photovoltaic yarn 1 can be manufactured. By carrying out the active layer lamination step, the conductive polymer layer lamination step, the thermoplastic resin layer lamination step, and the electron beam irradiation step in an inert gas atmosphere having an oxygen concentration of 1% or less, the active layer 3, the conductive polymer Oxygen that impairs power generation performance in the layer 4 and the thermoplastic resin layer 5 can be shielded. Furthermore, since it is possible to prevent the crosslinking reaction of the thermoplastic resin layer 5 from being inhibited in the electron beam irradiation step, the photovoltaic yarn 1 having excellent durability can be manufactured.

本発明に係わる光発電糸１の製造方法において、活性層積層工程から電子線照射工程までの処理を、酸素濃度１％以下の不活性ガス雰囲気下で行う。前記不活性ガス雰囲気とは、導電糸２の周囲に中心側から順に積層した活性層３、導電性高分子層４及び熱可塑性樹脂層５において発電性能を損わないようにするために窒素置換などで酸素濃度を１％以下にした状態である。また、活性層積層工程から熱可塑性樹脂層積層工程までの各積層工程は、精度良く均一に積層する方法を用いれば良く、例えばダイコート法、ディップコート法を挙げることができる。   In the manufacturing method of the photovoltaic yarn 1 concerning this invention, the process from an active layer lamination process to an electron beam irradiation process is performed in inert gas atmosphere with an oxygen concentration of 1% or less. The inert gas atmosphere is nitrogen substitution in order not to impair power generation performance in the active layer 3, the conductive polymer layer 4, and the thermoplastic resin layer 5 that are sequentially laminated around the conductive yarn 2 from the center side. Thus, the oxygen concentration is 1% or less. Moreover, each lamination process from an active layer lamination process to a thermoplastic resin layer lamination process should just use the method of laminating accurately and uniformly, for example, can mention the die-coating method and the dip-coating method.

（活性層積層工程）
活性層積層工程では、ポリチオフェン誘導体とフラーレン誘導体を溶媒に溶解した混合溶液を、例えばダイコート法で塗工することで、導電糸２の周囲に精度良く積層することができる。溶媒としては特に限定されないが、例えばジクロロベンゼン、クロロベンゼン、トルエンを挙げることができる。積層する活性層３の厚さは特に限定されないが、２０ｎｍ〜１５００ｎｍの範囲が好ましい。活性層３の厚さが２０ｎｍ未満では電荷分離が発生し難くなるので発電性能の低下を招くため好ましくない。１５００ｎｍを超えると活性層内で電荷の移動に対する抵抗が大きくなるので発電性能の低下を招くため好ましくない。 (Active layer lamination process)
In the active layer laminating step, a mixed solution in which a polythiophene derivative and a fullerene derivative are dissolved in a solvent is applied by, for example, a die coating method, whereby the conductive yarn 2 can be accurately laminated. Although it does not specifically limit as a solvent, For example, a dichlorobenzene, chlorobenzene, and toluene can be mentioned. Although the thickness of the active layer 3 to laminate | stack is not specifically limited, The range of 20 nm-1500 nm is preferable. If the thickness of the active layer 3 is less than 20 nm, it is difficult to generate charge separation, which is not preferable because power generation performance is reduced. If the thickness exceeds 1500 nm, the resistance to charge movement in the active layer increases, and this causes a decrease in power generation performance.

（導電性高分子層積層工程）
導電性高分子層積層工程では、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）にポリスチレンスルホン酸（ＰＳＳ）がドープされた混合物、またはポリアニリン（ＰＡＮＩ）にポリスチレンスルホン酸（ＰＳＳ）がドープされた混合物を水に分散させた分散溶液を、例えばダイコート法で塗工することで、活性層３の周囲に精度良く積層することができる。積層する導電性高分子層４の厚みは特に限定されない。必要な発電性能に基づいて厚みを調整すれば良い。 (Conductive polymer layer lamination process)
In the conductive polymer layer laminating step, a mixture of polyethylene dioxythiophene (PEDOT) doped with polystyrene sulfonic acid (PSS) or polyaniline (PANI) doped with polystyrene sulfonic acid (PSS) is dispersed in water. By applying the dispersed solution, for example, by a die coating method, the active layer 3 can be accurately laminated around the active layer 3. The thickness of the conductive polymer layer 4 to be laminated is not particularly limited. The thickness may be adjusted based on the required power generation performance.

（熱可塑性樹脂層積層工程）
熱可塑性樹脂層積層工程では、融点温度以上に加熱されたＥＶＡ（エチレン−酢酸ビニル共重合樹脂）、またはＰＶＢ（ポリビニルブチラール樹脂）を、例えばダイコート法で塗工することで、導電性高分子層４の周囲に精度良く積層することができる。積層する熱可塑性樹脂層５の厚さは特に限定されないが、１００ｎｍ〜５００００ｎｍの範囲が好ましい。熱可塑性樹脂層５の厚さが１００ｎｍ未満では酸素及び水分に対する遮蔽力が充分とはいえなくなり発電性能の低下を招くため好ましくない。５００００ｎｍを超えると光発電糸の柔軟性を損なうため好ましくない。 (Thermoplastic resin layer lamination process)
In the thermoplastic resin layer laminating step, the conductive polymer layer is formed by applying EVA (ethylene-vinyl acetate copolymer resin) or PVB (polyvinyl butyral resin) heated to a temperature equal to or higher than the melting point temperature by, for example, a die coating method. 4 can be laminated with high precision. Although the thickness of the thermoplastic resin layer 5 to laminate | stack is not specifically limited, The range of 100 nm-50000 nm is preferable. If the thickness of the thermoplastic resin layer 5 is less than 100 nm, the shielding ability against oxygen and moisture cannot be said to be sufficient, and the power generation performance is lowered, which is not preferable. If it exceeds 50000 nm, the flexibility of the photovoltaic yarn is impaired, which is not preferable.

（電子線照射工程）
電子線照射工程では、照射量が５０ｋＧｙ〜２５０ｋＧｙの範囲の電子線を照射する。熱可塑性樹脂層５に５０ｋＧｙ〜２５０ｋＧｙの範囲の電子線を照射することで、熱可塑性樹脂層５を架橋反応により耐久性に優れた層とすることができる。照射量が５０ｋＧｙ未満では架橋反応が進まず、照射量が２５０ｋＧｙを超えると、電子線が導電性高分子層４及び活性層３にまで達し、導電性高分子層４及び活性層３を破壊してしまうため発電性能の低下を招くおそれがある。 (Electron beam irradiation process)
In the electron beam irradiation step, an electron beam with an irradiation dose in the range of 50 kGy to 250 kGy is irradiated. By irradiating the thermoplastic resin layer 5 with an electron beam in the range of 50 kGy to 250 kGy, the thermoplastic resin layer 5 can be made into a layer having excellent durability by a crosslinking reaction. When the irradiation dose is less than 50 kGy, the crosslinking reaction does not proceed. When the irradiation dose exceeds 250 kGy, the electron beam reaches the conductive polymer layer 4 and the active layer 3 to destroy the conductive polymer layer 4 and the active layer 3. As a result, power generation performance may be reduced.

次に、本発明の具体的実施例について説明するが、本発明はこれらの実施例のものに特に限定されるものではない。なお、試験方法及び評価は次の通りである。   Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples. The test method and evaluation are as follows.

（耐光強伸度試験）
８０℃±３℃の雰囲気下にてＪＩＳ Ｂ ７７５３に準じたサンシャインウェザーメータＳ８０（スガ試験機株式会社製）を用い、ＪＩＳ Ｃ８９１５に準じて２０００時間露光し、オートグラフＡＧ−１ＫＮ（株式会社島津製作所）を用いて、ＪＩＳ Ｌ １０１５に準じて光発電糸の引張り強さ及び伸び率の変化を測定した。耐候試験後の強伸度変化が１０％以内を「○」、強伸度変化が１０％を超えたものを「×」で表し、「○」を合格とした。 (Light strong elongation test)
Using an sunshine weather meter S80 (made by Suga Test Instruments Co., Ltd.) according to JIS B 7753 in an atmosphere of 80 ° C. ± 3 ° C., exposure was performed for 2000 hours according to JIS C8915, and Autograph AG-1KN (Shimadzu Corporation) The change in tensile strength and elongation of the photovoltaic yarn was measured according to JIS L 1015. A change in strong elongation after the weather resistance test within 10% was indicated by “◯”, a change in strength change exceeding 10% was indicated by “x”, and “◯” was regarded as acceptable.

（摩擦堅牢度試験）
JIS L ０８４９に準じた摩擦試験機II形を用い、１４ｃｍ×５ｃｍの厚紙に光発電糸１を重ならないように３ｃｍ幅で長手方向に巻きつけた試験片を試験し評価した。導電性高分子層４の摩擦用白綿布への着色を目視で評価した。着色が認められなかったものを「○」、僅かに認められたものを「△」、着色が認められたものを「×」で表し、「○」を合格とした。 (Friction fastness test)
Using a friction tester type II conforming to JIS L 0849, a test piece wound in the longitudinal direction with a width of 3 cm so as not to overlap the 14 cm × 5 cm thick paper with the photovoltaic yarn 1 was tested and evaluated. The coloring of the conductive polymer layer 4 on the white cotton cloth for friction was visually evaluated. The case where coloring was not recognized was represented by “◯”, the case where slight coloring was observed was represented by “Δ”, the case where coloring was observed was represented by “x”, and “◯” was regarded as passing.

＜実施例１＞
酸素濃度０．１％の窒素ガス雰囲気下で、導電糸２として用意した直径１００μｍのアルミニウム蒸着ポリエステル糸の周囲に、ポリ−３−ヘキシルチオフェン（Ｐ３ＨＴ）とアクセプターとしてフェニルＣ６１ブチル酸メチルエステル（ＰＣＢＭ）をトルエン溶媒に溶解し混合液をダイコート法にて厚み１５０ｎｍになるように塗工した後、１５０℃×２０分緩やかに加熱し溶媒を揮発させ活性層３を積層した。次に、活性層３の周囲にポリエチレンジオキシチオフェン（ＰＥＤＯＴ）にポリスチレンスルホン酸（ＰＳＳ）をドープさせた水分散体をダイコート法にて厚み１５０ｎｍになるように塗工した後、２００℃×２０分加熱し水分を乾燥させ導電性高分子層４を積層した。さらに、導電性高分子層４の周囲に１８０℃で溶融した熱可塑性樹脂ＥＶＡ（エチレン−ビニル共重合樹脂）をダイコート法にて厚み８０００ｎｍになるように塗工し、２０℃の室温の中で空冷して熱可塑性樹脂層５を積層した。最後に、照射量１００ｋＧｙの電子線を熱可塑性樹脂層５に照射して熱可塑性樹脂層５の架橋を促進、硬化させて光発電糸１を得た。 <Example 1>
In an atmosphere of nitrogen gas with an oxygen concentration of 0.1%, poly-3-hexylthiophene (P3HT) and phenyl C 61 butyric acid methyl ester (acceptor) as an acceptor are provided around an aluminum-deposited polyester yarn having a diameter of 100 μm prepared as a conductive yarn 2. PCBM) was dissolved in a toluene solvent, and the mixed solution was applied by a die coating method so as to have a thickness of 150 nm, and then heated gently at 150 ° C. for 20 minutes to evaporate the solvent, and the active layer 3 was laminated. Next, an aqueous dispersion obtained by doping polyethylene dioxythiophene (PEDOT) with polystyrene sulfonic acid (PSS) around the active layer 3 is coated to a thickness of 150 nm by a die coating method, and then 200 ° C. × 20 The mixture was heated for a minute to dry the moisture, and the conductive polymer layer 4 was laminated. Further, a thermoplastic resin EVA (ethylene-vinyl copolymer resin) melted at 180 ° C. around the conductive polymer layer 4 is applied by a die coating method to a thickness of 8000 nm, and at a room temperature of 20 ° C. The thermoplastic resin layer 5 was laminated by air cooling. Finally, the thermoplastic resin layer 5 was irradiated with an electron beam with an irradiation amount of 100 kGy to promote and cure the crosslinking of the thermoplastic resin layer 5 to obtain the photovoltaic yarn 1.

＜実施例２＞
熱可塑性樹脂ＥＶＡ（エチレン−ビニル共重合樹脂）を厚み１００００ｎｍになるように塗工したことと、熱可塑性樹脂層５に照射した電子線の照射量を８０ｋＧｙとしたこと以外は実施例１と同様にして光発電糸１を得た。 <Example 2>
The same as in Example 1 except that the thermoplastic resin EVA (ethylene-vinyl copolymer resin) was applied to a thickness of 10,000 nm and that the irradiation amount of the electron beam applied to the thermoplastic resin layer 5 was 80 kGy. Thus, a photovoltaic yarn 1 was obtained.

＜実施例３＞
酸素濃度０．５％の窒素ガス雰囲気下で実施したことと、導電糸２として直径２００μｍのステンレス鋼繊維を用いたことと、熱可塑性樹脂ＥＶＡ（エチレン−ビニル共重合樹脂）を厚み２００００ｎｍになるように塗工したこと以外は実施例１と同様にして光発電糸１を得た。 <Example 3>
It was carried out in a nitrogen gas atmosphere with an oxygen concentration of 0.5%, a stainless steel fiber having a diameter of 200 μm was used as the conductive yarn 2, and a thermoplastic resin EVA (ethylene-vinyl copolymer resin) having a thickness of 20000 nm. A photovoltaic yarn 1 was obtained in the same manner as in Example 1 except that coating was performed as described above.

＜実施例４＞
活性層３としてポリ−３−オクチルチオフェン（Ｐ３ＯＴ）、ポリ−３−ドデシルチオフェン（Ｐ３ＤＤＴ）をトルエン溶媒に溶解し混合液をダイコート法にて厚み２００ｎｍになるように塗工したことと、熱可塑性樹脂ＥＶＡ（エチレン−ビニル共重合樹脂）を厚み１００００ｎｍになるように塗工したことと、熱可塑性樹脂層５に照射した電子線の照射量を２００ｋＧｙとしたこと以外は実施例１と同様にして光発電糸１を得た。 <Example 4>
As active layer 3, poly-3-octylthiophene (P3OT) and poly-3-dodecylthiophene (P3DDT) were dissolved in a toluene solvent, and the mixture was applied to a thickness of 200 nm by a die coating method, and thermoplasticity Except that the resin EVA (ethylene-vinyl copolymer resin) was applied to a thickness of 10000 nm and the irradiation amount of the electron beam applied to the thermoplastic resin layer 5 was 200 kGy, the same as in Example 1. A photovoltaic yarn 1 was obtained.

＜実施例５＞
酸素濃度０．３％の窒素ガス雰囲気下で実施したことと、導電性高分子層４としてポリアニリン（ＰＡＮＩ）にポリスチレンスルホン酸（ＰＳＳ）をドープさせた水分散体を厚み１００ｎｍになるように塗工したことと、熱可塑性樹脂ＥＶＡ（エチレン−ビニル共重合樹脂）を厚み１５０００ｎｍになるように塗工したこと以外は実施例１と同様にして光発電糸１を得た。 <Example 5>
It was carried out in a nitrogen gas atmosphere with an oxygen concentration of 0.3%, and an aqueous dispersion in which polyaniline (PANI) was doped with polystyrene sulfonic acid (PSS) as the conductive polymer layer 4 was applied to a thickness of 100 nm. A photovoltaic yarn 1 was obtained in the same manner as in Example 1 except that it was coated and a thermoplastic resin EVA (ethylene-vinyl copolymer resin) was applied to a thickness of 15000 nm.

＜実施例６＞
熱可塑性樹脂ＰＶＢ（ポリビニルブチラール樹脂）を厚み１５０００ｎｍになるように塗工熱可塑性樹脂層５に照射した電子線の照射量を１５０ｋＧｙとしたこと以外は実施例１と同様にして光発電糸１を得た。 <Example 6>
The photovoltaic yarn 1 is formed in the same manner as in Example 1 except that the irradiation amount of the electron beam applied to the coating thermoplastic resin layer 5 is 150 kGy so that the thickness of the thermoplastic resin PVB (polyvinyl butyral resin) is 15000 nm. Obtained.

＜比較例１＞
熱可塑性樹脂ＥＶＡ（エチレン−ビニル共重合樹脂）を厚み６００００ｎｍになるように塗工したこと以外は実施例１と同様にして光発電糸１を得た。 <Comparative Example 1>
Photovoltaic yarn 1 was obtained in the same manner as in Example 1 except that thermoplastic resin EVA (ethylene-vinyl copolymer resin) was applied to a thickness of 60000 nm.

＜比較例２＞
酸素濃度１０％の窒素ガス雰囲気下で実施したこと以外は実施例２と同様にして光発電糸１を得た。 <Comparative example 2>
Photovoltaic yarn 1 was obtained in the same manner as in Example 2 except that it was carried out in a nitrogen gas atmosphere with an oxygen concentration of 10%.

＜比較例３＞
電子線を照射しなかった以外は実施例３と同様にして光発電糸１を得た。 <Comparative Example 3>
A photovoltaic yarn 1 was obtained in the same manner as in Example 3 except that the electron beam was not irradiated.

＜比較例４＞
熱可塑性樹脂にアクリル樹脂を厚み１００００ｎｍになるように塗工したこと以外は実施例４と同様にして光発電糸１を得た。 <Comparative example 4>
Photovoltaic yarn 1 was obtained in the same manner as in Example 4 except that an acrylic resin was applied to the thermoplastic resin to a thickness of 10,000 nm.

実施例１〜６及び比較例１〜４と評価結果を表１に示す。
Tables 1 to 6 and Comparative Examples 1 to 4 and the evaluation results are shown in Table 1.

本発明に係わる光発電糸の一実施形態を示す概略断面図である。It is a schematic sectional drawing which shows one Embodiment of the photovoltaic yarn concerning this invention.

１・・・光発電糸
２・・・導電糸
３・・・活性層
４・・・導電性高分子層
５・・・熱可塑性樹脂層 DESCRIPTION OF SYMBOLS 1 ... Photoelectric generation yarn 2 ... Conductive yarn 3 ... Active layer 4 ... Conductive polymer layer 5 ... Thermoplastic resin layer

本発明に係る光発電糸は、例えば製編あるいは製織し布帛にすることで、太陽光発電に応用できる。   The photovoltaic yarn according to the present invention can be applied to photovoltaic power generation, for example, by knitting or weaving into a fabric.

Claims (8)

導電糸の周囲に中心側から順に、活性層、導電性高分子層及び熱可塑性樹脂層が積層された光発電糸において、該熱可塑性樹脂層の厚さが０．１μｍ〜５０μｍ、かつ、該熱可塑性樹脂層の厚さが前記導電糸の直径に対して１／２０〜１／５であることを特徴とする光発電糸。 In the photovoltaic yarn in which the active layer, the conductive polymer layer, and the thermoplastic resin layer are laminated in order from the center side around the conductive yarn, the thickness of the thermoplastic resin layer is 0.1 μm to 50 μm, and The photovoltaic yarn, wherein the thermoplastic resin layer has a thickness of 1/20 to 1/5 of the diameter of the conductive yarn. 前記活性層が、ポリチオフェン誘導体及びフラーレン誘導体からなる請求項１に記載の光発電糸。 The photovoltaic yarn according to claim 1, wherein the active layer is composed of a polythiophene derivative and a fullerene derivative. 前記導電性高分子層が、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）／ポリスチレンスルホン酸（ＰＳＳ）、ポリアニリン（ＰＡＮＩ）／ポリスチレンスルホン酸ＰＳＳから選ばれる１種である請求項１または２に記載の光発電糸。 The photovoltaic yarn according to claim 1 or 2, wherein the conductive polymer layer is one selected from polyethylene dioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS) and polyaniline (PANI) / polystyrene sulfonic acid PSS. . 前記熱可塑性樹脂層が、ＥＶＡ（エチレン−酢酸ビニル共重合樹脂）、ＰＶＢ（ポリビニルブチラール樹脂）から選ばれる１種である請求項１〜３のいずれか１項に記載の光発電糸。 The photovoltaic yarn according to any one of claims 1 to 3, wherein the thermoplastic resin layer is one selected from EVA (ethylene-vinyl acetate copolymer resin) and PVB (polyvinyl butyral resin). 酸素濃度１％以下の不活性ガス雰囲気下で、導電糸の周囲に活性層を塗工し乾燥することにより活性層を得る活性層積層工程と、前記活性層の周囲に導電性高分子層を塗工し乾燥することにより導電性高分子層を得る導電性高分子層積層工程と、前記導電性高分子層の周囲に熱可塑性樹脂層を塗工することにより該熱可塑性樹脂層の厚さが０．１μｍ〜５０μｍ、かつ、該熱可塑性樹脂層の厚さが前記導電糸の直径に対して１／２０〜１／５である熱可塑性樹脂層を得る熱可塑性樹脂層積層工程と、前記熱可塑性樹脂層に５０ｋＧｙ〜２５０ｋＧｙの範囲の電子線照射を行う電子線照射工程とを順に実施することを特徴とする光発電糸の製造方法。 In an inert gas atmosphere with an oxygen concentration of 1% or less, an active layer laminating step for obtaining an active layer by coating and drying the active layer around the conductive yarn, and a conductive polymer layer around the active layer A conductive polymer layer laminating step for obtaining a conductive polymer layer by coating and drying, and a thickness of the thermoplastic resin layer by coating a thermoplastic resin layer around the conductive polymer layer A thermoplastic resin layer laminating step of obtaining a thermoplastic resin layer having a thickness of 0.1 μm to 50 μm and a thickness of the thermoplastic resin layer of 1/20 to 1/5 of the diameter of the conductive yarn, The manufacturing method of the photovoltaic yarn characterized by implementing in order the electron beam irradiation process of performing the electron beam irradiation of the range of 50 kGy-250 kGy to a thermoplastic resin layer. 前記活性層積層工程において、前記活性層としてポリチオフェン誘導体及びフラーレン誘導体を用いる請求項５に記載の光発電糸の製造方法。 The method for producing a photovoltaic yarn according to claim 5, wherein a polythiophene derivative and a fullerene derivative are used as the active layer in the active layer lamination step. 前記導電性高分子層積層工程において、前記導電性高分子層としてポリエチレンジオキシチオフェン（ＰＥＤＯＴ）／ポリスチレンスルホン酸（ＰＳＳ）、ポリアニリン（ＰＡＮＩ）／ポリスチレンスルホン酸ＰＳＳから選ばれる１種を用いる請求項５または６に記載の光発電糸の製造方法。 The conductive polymer layer laminating step uses one kind selected from polyethylene dioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS) and polyaniline (PANI) / polystyrene sulfonic acid PSS as the conductive polymer layer. A method for producing a photovoltaic yarn according to 5 or 6. 前記熱可塑性樹脂層積層工程において、前記熱可塑性樹脂としてＥＶＡ（エチレン−酢酸ビニル共重合樹脂）、ＰＶＢ（ポリビニルブチラール樹脂）から選ばれる１種を用いる請求項５〜７のいずれか１項に記載の光発電糸の製造方法。 In the said thermoplastic resin layer lamination process, 1 type chosen from EVA (ethylene-vinyl acetate copolymer resin) and PVB (polyvinyl butyral resin) is used as said thermoplastic resin. Manufacturing method of photovoltaic power yarn.
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