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TW201133901A - Guard substrate for optical electromotive force equipment, and its production process - Google Patents

Guard substrate for optical electromotive force equipment, and its production process Download PDF

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Publication number
TW201133901A
TW201133901A TW099122987A TW99122987A TW201133901A TW 201133901 A TW201133901 A TW 201133901A TW 099122987 A TW099122987 A TW 099122987A TW 99122987 A TW99122987 A TW 99122987A TW 201133901 A TW201133901 A TW 201133901A
Authority
TW
Taiwan
Prior art keywords
substrate
photovoltaic device
transparent
protective substrate
resin
Prior art date
Application number
TW099122987A
Other languages
Chinese (zh)
Inventor
Yasukazu Kishimoto
Takayuki Mori
Toru Yoshida
Original Assignee
Kisco Ltd
Tosoh F Tech Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kisco Ltd, Tosoh F Tech Inc filed Critical Kisco Ltd
Publication of TW201133901A publication Critical patent/TW201133901A/en

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
    • H10F77/315—Coatings for devices having potential barriers for photovoltaic cells the coatings being antireflective or having enhancing optical properties
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/40—Optical elements or arrangements
    • H10F77/42—Optical elements or arrangements directly associated or integrated with photovoltaic cells, e.g. light-reflecting means or light-concentrating means
    • H10F77/484—Refractive light-concentrating means, e.g. lenses
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/40—Optical elements or arrangements
    • H10F77/42—Optical elements or arrangements directly associated or integrated with photovoltaic cells, e.g. light-reflecting means or light-concentrating means
    • H10F77/488—Reflecting light-concentrating means, e.g. parabolic mirrors or concentrators using total internal reflection
    • 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
    • Y02E10/52—PV systems with concentrators

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  • Photovoltaic Devices (AREA)

Abstract

To provide a protective substrate for photovoltaic device, wherein the protective substrate is suitable for constituting the photovoltaic device higher in photoelectric conversion efficiency than a conventional structure; and to provide a method of manufacturing the same. The protective substrate for photovoltaic device is constructed such that a fine uneven structure 102 is formed on one surface of a transparent substrate 101, the area of a part which is not more than 60[deg.] in angle between a tangent of a protruded surface constituting the fine uneven structure 102 and a normal relative to a substrate surface is at least 5% of the entire area of the fine uneven structure, the form of the protruded part is approximate to the form of a section partially cut out of a sphere, and the relation between the radius A of curvature of the protruded part and the radius B of the approximate circle of the cut-out section is expressed by a formula B≥A/2.

Description

201133901 六、發明說明： 【發明所屬之技術領域】 本發明係關於光電動勢裝置用保護基板及其製造方法 ’尤其關於外部光的反射率小’取光效率良好之光電動勢 裝置用保護基板及其製造方法。 【先前技術】 當受到光照射時會產生電動勢之光電動勢裝置，係使 用在作爲用以解決火力發電廠、水力發電廠、核能發電廠 等之既存發電方法的環境問題之替代能源而受到矚目之太 陽光發電系統等。此太陽光發電系統，一般稱爲太陽能電 池’目前太陽能電池的最大課題之一爲發電效率低之問題 。關於用以提升發電效率之手法，以往係已探討各種手法 ，但主要仍集中在提升太陽能電池本身的光/電轉換效率 (光電轉換效率）本身者。 太陽能電池模組，爲了保護單元，係於單元表面上具 有玻璃或透明樹脂薄膜之表面保護構件，但關於此部分， 用以提升發電效率之對策可說是尙未完備。通常，此透明 保護構件上並未施以任何處理。使用此類一般的保護構件 之太陽能電池模組，例如爲玻璃基板時，會在該表面使3 -4%程度的太陽光反射。此反射光完全無益於發電，故成爲 使太陽能電池模組的發電效率降低之一大因素。 日本特開平9-1 9 1 1 1 5號公報（專利文獻1 )中，係揭 示下列太陽能電池模組，亦即將含浸有具有預定大小的間 -5- 201133901 距的凹凸之纖維狀無機化合物之透明有機高分子樹脂（ EVA等）配置在光電動勢元件的光入射側，藉此防止反射 光到達其他住宅或地面並使位於該處的人感到眩目不舒服 之問題，使透明有機高分子樹脂的鈹折變得不醒目，防止 髒污附著於表面，並且能夠承受長期間的屋外使用之太陽 能電池模組。 然而，此文獻之凹凸構造的目的在於用以防止上述眩 目以及髒污的附著者，對於爲了改善發電效率而防止表面 反射者並未進行探討。此外，此文獻中，爲了在被覆材表 面設置凹凸，係將纖維狀無機化合物含浸於透明有機高分 子樹脂，但此具體而言爲使用玻璃纖維不織布、玻璃纖維 織布、玻璃塡充材等。然而，此需具備將此等纖維分散含 浸於樹脂之程序，且亦需嚴密地管理分散程度位於評定範 圍內者，不僅量產程序上伴隨著困難度，且製造成本亦上 升。再者，此纖維在長期使用下，亦需進行用以與樹脂材 料之間確保充分的密著力之底層處理，此亦成爲步驟增加 之因素。 日本特開2008-260654號公報（專利文獻2 )中，係揭 示下列手法，亦即使用將高折射率與低折射率的薄膜層予 以組合並層合於覆蓋玻璃的表裏兩面或僅爲表面上之手法 ，藉此抑制太陽能電池單元可有效地進行光電轉換之波長 區域的反射，而提升光穿透量之手法。 然而，此文獻的手法中，係藉由折射率不同之各薄膜 層的組合來獲得反射抑制效果，故無法期待其抑制在表面 -6 - 201133901 本身產生反射的光’或是相對於入射角較小的光之改善效 果。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開平9_191115號公報 [專利文獻2]日本特開2008-260654號公報 【發明內容】 (發明所欲解決之課題） 所欲解決之問題點，在於提供一種耐氣候性與耐久性 高’容易製造且可提升聚光效率，並且最適合於構成光電 轉換效率較以往構造更高之光電動勢裝置之光電動勢裝置 用保護基板及其製造方法。 (用以解決課題之手段） 以往用作爲太陽能電池單元保護用之玻璃或透明樹脂 膜，其折射率爲1 · 5以上，與大氣（空氣）之折射率差較 大，所以具有在表面上的折射率大之問題。當以空氣的折 射率爲1.00，以玻璃的折射率爲1.52時之光的入射角與玻 璃表面的反射率之關係，係如下列表所示。表中的折射角 ，爲以玻璃平面的法線方向作爲入射角0度時之角度。 201133901 [第1表] （。2__0 15 30 45 60 75 90 反射率（％) 4.3 4.7 6.1 9.7 18 41 〇 從第1表中可得知，爲玻璃時，即使是垂直入射（〇度 )’亦有4%以上的光產生反射。此外，斜向入射之光中， 其反射更大’例如當入射角爲70度時，反射率爲30%以上 。因此，尤其針對斜向入射於基板表面之光的反射光，必 須採取對策。 爲了解決上述課題，本發明係採用下列構成。 (1) 一種光電動勢裝置用保護基板，其係具有：於 配置在感光部之透明基板的表面上具有凹凸構造之透明樹 脂層；該透明樹脂層的折射率係與前述透明基板的折射率 相同或以下。 (2) 如上述（1)之光電動勢裝置用保護基板，其中 前述透明基板係由玻璃所形成。 (3) 如上述（1)或（2)之光電動勢裝置用保護基 板’其中前述透明樹脂層係藉由樹脂或樹脂及無機物所形 成。 (4) 如上述（1)〜（3)中任一項之光電動勢裝置用 保護基板，其中構成前述凹凸構造之凸部面的切線與相對 於基板面之法線所成的角爲60度以下之部分的面積爲全部 凹凸構造面積的5%以上。 (5) 如上述（Π〜（4)中任一項之光電動勢裝置用 -8 - 201133901 保護基板’其中前述凹凸構造在前述透明基板的法線方向 上之剖面形狀爲近似於圓的一部分之形狀或近似於三角形 之形狀，此等之底面的大小，以直徑表示時爲2〇〇nm、 ΙΟΟΟμηι，凸部的數目係每1平方公分爲1~2.5χ109個。 (6) 如上述（1)〜（5)中任一項之光電動勢裝置用 保護基板，其中前述凹凸的平均大小爲2mm以下。 (7) 如上述（1)〜（5)中任一項之光電動勢裝置用 保護基板，其中前述透明樹脂層係具有熱或光硬化樹脂。 (8) —種光電動勢裝置用保護基板的製造方法，其 係將折射率與透明基板相同或以下之透明樹脂層合於配置 在感光部之透明基板上，將細微的凹凸形成於前述透明樹 脂層的表面，在形成中或形成後的任一階段中使透明樹脂 層硬化，將細微的凹凸構造形成於此透明樹脂層的表面。 (9) 如上述（8)之光電動勢裝置用保護基板的製造 方法，其係將形成有細微凹凸之模具或線狀的構件予以組 合來按壓前述透明樹脂層的表面，或以具有突起或鈎之剛 性體來連續地按壓或切削，藉此形成凹部而成形爲凹凸。 (10) 如上述（8)之光電動勢裝置用保護基板的製 造方法，其中在層合前述透明樹脂後，藉由光罩法或光成 形法成形爲凹凸。 (11) 如上述（8)之光電動勢裝置用保護基板的製 造方法，其係藉由印刷法將前述透明樹脂層合於細微的凹 凸圖型而形成爲凹凸。 (12) 如上述（8)之光電動勢裝置用保護基板的製 -9 - 201133901 造方法’其係將前述樹脂材料塗佈於透明基板上並形成細 微的凹凸構造。 (13) 如上述（12)之光電動勢裝置用保護基板的製 造方法，其中前述塗佈係藉由分注器或噴墨來進行。 (14) 如上述（8) ~(13)中任一項之光電動勢裝置 用保護基板的製造方法，其中透明樹脂層係具有熱或光硬 化樹脂》 (15) 如上述（8) ~(14)中任一項之光電動勢裝置 用保護基板的製造方法，其中構成前述細微凹凸構造之凸 部的形狀係近似於裁切球的一部分後之形狀， 此凸部的曲率半徑A與裁切後之切斷面的近似圓的半 徑B之關係，係由下列式（1 )所表示， B ^ A/2 ( 1 )。 發明之效果： 根據本發明，由於透明樹脂的折射率低，所以可較玻 璃與PET ·聚乙烯等之高分子膜更爲降低反射率。除此之 外，由於形成立體的細微凹凸紋理構造，所以更能夠降低 反射率，而提供一種最適合於構成光電轉換效率較以往構 造更高之光電動勢裝置之光電動勢裝置用保護基板及其製 造方法。 此外，根據本發明之光電動勢裝置用保護基板的製造 方法，能夠以簡單的構成且低成本連續地製造細微凹凸構 造，對於在量產步驟中製造出光電動勢裝置用保護基板者 -10- 201133901 ，乃極爲有用。 【實施方式】 本發明之光電動勢裝置用保護基板，係於配置在光電 動勢裝置的感光部之透明基板的表面上，設置具有細微的 凹凸之透明樹脂層。以下係參照圖面，說明本發明之一項 實施型態。 第1圖爲本發明之光電動勢裝置用保護基板的一構成 例。第1圖中，光電動勢裝置用保護基板，係具有：透明 基板1 〇 1，以及由形成在透明基板上之透明樹脂所構成之 細微凹凸紋理構造102。第2圖爲本發明之光電動勢裝置用 保護基板的其他構成例。第2圖中，光電動勢裝置用保護 基板，係具有：透明基板2 0 1，以及具有由形成在透明基 板上之透明樹脂所構成之細微凹凸紋理構造之透明樹脂層 202 ° 此外，如第3圖、第4圖所示，凹凸構造可爲近似於球 的一部分之形狀。第3圖、第4圖係顯示本發明之光電動勢 裝置用保護基板的第3、第4構成例之模式圖。第3圖中， 光電動勢裝置用保護基板，係具有：透明基板301，以及 形成在透明基板上之細微凹凸構造302。此外，第4圖中， 光電動勢裝置用保護基板，係具有：透明基板401，以及 具有在透明基板上形成有細微凹凸構造之細微凹凸構造層 402 - 形成在透明基板上之細微凹凸紋理構造，如第1圖、 -11 - 201133901 第3圖的例子般，可爲直接將細微凹凸構造3 02形成於透明 樹脂層的上部，且凹凸構造爲獨立之構造，或是如第2圖 、第4圖的例子般，將形成有細微凹凸構造之透明樹脂層 配置在基板上，並於透明樹脂層202、402的上部形成有細 微凹凸紋理之構造。 接著說明本發明之原理。第6圖、第7圖係顯示本發明 之原理之光電動勢裝置用保護基板的模式圖。本發明之細 微凹凸構造，所構成之凸部的剖面形狀，爲近似於圓的一 部分之形狀或近似於三角形之形狀。因此，縱向剖面及橫 向剖面爲四角形者被除外。第6圖中，係於基板1上形成有 本發明之細微凹凸構造2。此細微凹凸構造，在此例中係 爲了容易說明而將剖面形成爲三角形。 首先探討從垂直方向將光線L 1、L2、L3照射在此基板 之情況。光線L1、L2、L3，當到達細微凹凸構造2的斜面 時，其一部分穿透，其他部分反射。將此時的反射率設爲 4%。在此，當著眼於光線L2時，穿透光12爲入射光L2減去 反射光L2’的量，當入射於細微凹凸構造2中時，由於該材 料的折射率η，而偏向角度0n入射並穿透基板1並到達圖 中未顯示的單元。 另一方面，各反射光LI'、L2'、L3’入射於其他細微構 造，一部分更作爲反射光L 1 "、L2 ”、L3 "擴散至外部並散 失。在此，入射於其他細微構造之反射光L 1 ”的入射光1 Γ ，與前述相同，藉由該折射率0 η而偏向入射，再於其他 界面產生反射，成爲入射光1Γ'穿透基板並到達單元。與前 -12- 201133901 述相同，入射光的一部分，雖然圖中未顯示，但於前述 界面擴散至外部。其他反射光L2'、L3'亦相同，入射於其 他細微構造，且其一部分到達單元。 如此，藉由在基板表面設置細微構造，可將至目前爲 止所擴散至外部並散失之反射光的一部分予以導入並引導 至單元，有益於光電轉換效率並提升發電效率。此例中， 爲了容易說明而說明0 t爲45°之剖面三角形的構造，但此 時當光線的入射角爲45°時，難以藉由上述構造獲得效率 改善效果。因此，當剖面爲三角形狀時，必須考量設置環 境等來設計成最適角度。 接著參照第7圖來說明半球狀的細微凹凸構造之情況 。圖中’係於基板1上形成有本發明之細微凹凸構造2。此 細微凹凸構造’在此例中係以各凸部接觸之方式所接近而 形成爲半球狀。 首先假定從垂直方向將光線L 1、L2、L3照射在此基板 1。光線L1、L2、L3，當到達細微凹凸構造2的曲面時，與 上述相同’其一部分穿透，其他部分反射。在此，係將此 細微凹凸構造2的切線中之與相對於基板面的法線所成的 角0 t爲6 0度的切線設爲t，將與凸部曲線之交點設爲p。 當著眼於從點P入射於切線與法線所成的角爲較小之 區域之光線L 1時，穿透光1 1爲從入射光L 1扣除反射光L j , 的量’當入射於細微凹凸構造2中時，由於該材料的折射 率η’而偏向角度θη入射並穿透基板1並到達圖中未顯示 的單元。另一方面，反射光L1，再次入射於鄰接之細微凹 -13- 201133901 凸構造，與前述相同，扣除反射光後偏向0η，並穿透基 板1而到達單元。入射於球面之穿透光11、12、13，係以收 斂於特定焦點之方式而偏向。 接著著眼於從點Ρ入射於切線與法線所成的角爲較大 之區域之光線L2，從入射光L2扣除反射光L2'之穿透光12 ，當入射於細微凹凸構造2中時，由於該材料的折射率η, 而偏向角度0 η入射並穿透基板1並到達圖中未顯示的單元 。另一方面，由於反射光L2'已朝向上方的角度反射，故 不會再次入射於鄰接之細微凹凸構造而散失。此例中，係 探討來自與基板面呈垂直之方向的光，但在斜向入射於基 板面之光中，即使在從點Ρ入射於切線與法線所成的角爲 較大之區域，亦可能再次入射於凹凸構造。然而，與從點 Ρ入射於切線與法線所成的角爲較小之區域相比，在較大 之區域中，反射光不會再次入射而散失之機率較高。 如此，即使形成曲面的細微凹凸構造，亦可使反射光 的一部分再入射而有效地活用。此外，與三角形的凹凸相 比，與各種入射光平行或垂直之面極少，使入射光所造成 之效率的變化較少。 細微凹凸紋理的形狀，並不限定於四角錐或圓錐或是 半球狀等之幾何學構造，亦可形成爲圓筒型或多角柱型等 之種種形狀。此外，可藉由具有垂直面或斜面來降低斜向 入射角，以提升聚光效率。因此，本發明中，尤其是凹凸 構造的形狀，可形成爲基板面的法線方向上之剖面近似於 圓的一部分之形狀，或是剖面近似於三角形之形狀。亦即 -14- 201133901 ’外形爲裁切球的一部分後之形狀或是近似於圓錐形之形 狀。此等形狀係容易形成，就製造工序方面來看亦爲有利 0 本發明中，當形成凹凸構造之斜面的角度，以基材之 法線方向的角度爲0時具有6 0度以下之傾斜角度的部分時 ’於該斜面所反射之光會到達其他斜面並成爲折射光，而 使光更有效地作用。因此，構成細微凹凸構造的凸部之面 ’較佳係以一定比率具有該切線與相對於基板面之法線所 成的角爲60度以下之部分。具體而言，前述成爲60度以下 之部分的面積爲全部細微凹凸構造面積的5%以上，更佳爲 2 〇 %以上，特佳爲3 0 %以上。設爲5 %以上者，是由於當考 量到在兩端具有全面積的2 · 5 %的傾斜部之梯形狀的凹凸構 造時，可期望達到約2%之入射光量的增加，而獲得0.01 % 的增益提升效果之故。此外，當細微凹凸構造的凸部形狀 近似於半球形時，前述面積的上限値約爲50%。 所謂構成前述凸部之面的切線，例如爲第8圖所示， 當考量到半球狀的凸部時，此半球的剖面形狀2’成爲半圓 形。相對於此半圓之切線P 1、P2，爲構成凸部之面的切線 ，爲相對於凸部剖面之切線。此外，相對於基板面Γ之法 線P0與前述切線所成的角爲上述角度。此角度爲法線p〇與 前述切線所成的角當中之銳角側的角度。此外，此等係判 斷爲不與前述凸部剖面爲同一剖面。 構成本發明的細微凹凸構造之凸部的形狀，可形成爲 剖面近似於圓形的一部分之形狀，亦即近似於裁切球的一 -15- 201133901 部分後之形狀。通常，所形成之凸部並非接近於正球狀， 較多爲變形後的球狀’但難以直接評估此般形狀。因此， 當評估凸部時’係考量爲使其近似於球的一部分。近似的 手法’例如可藉由圖像解析等將剖面置換爲等效面積之圓 形的一部分’或是置換爲外形最爲近似之圓形的一部分。 此外，使三角錐等之剖面近似於三角形的形狀時亦相同。 近似於球的一部分之凸部的曲率半徑A與裁切後之切 斷面的近似圓的半徑B之關係，係由下列式（1 )所表示。 B ^ A/2 ( 1 ) 所謂凸部的曲率半徑A，如上述般，爲近似於球的一 部分之凸部剖面形狀的曲率半徑。此外，所謂裁切後之切 斷面的近似圓，爲使凸部近似於裁切球的一部分後之形狀 時之裁切部分的形狀，由於此部分亦近似於圓，故定義爲 近似圓。近似圓的半徑B，較佳爲曲率半徑A的1 / 2以上， 亦即滿足上述式之關係。 例如爲第9圖所示，當凸部爲半球形時，該剖面爲半 圓形。此半圓的曲率半徑與作爲凸部的基部之切斷面的近 似圓的半徑B 1相等，成爲B = A。然而，即使是具有相同曲 率半徑之球形，隨著所裁切的部分變小，切斷面的近似圓 的半徑變成較小的B2、B3、B4。切斷面的近似圓的半徑 B4，正好爲曲率半徑A的1/2。當成爲較此更小之切斷面的 近似圓的半徑B 5時，所裁切的球形變得極小，無法過於期 待作爲細微凹凸構造的效果。因此，如滿足上述式的關係 般，係將切斷面的近似圓的半徑B5規定爲曲率半徑A的1/2 -16- 201133901 以上。此外，較佳爲B g 2A/3，尤佳爲B 2 3A/4，特佳爲B 2 4A/5。凸部形狀愈接近半球形，愈容易獲得效率提升效 果。另一方面，當B的大小某種程度愈接近A，即使更進一 步近似，亦無法過於期待提升效果。 細微凹凸構造的大小亦無特別限定，但當高度的平均 大小爲2mm以上時，會有因斜向入射光導致光害之疑慮。 此外，個別大小可具有變動度。此外，當細微凹凸紋理的 大小爲光的波長以下時，折射率在厚度方向上連續地變化 ，可顯現出存在折射率差的界面被消除之光學效果。 各個凸部（點）的大小並無特別限定，可因應樹脂的 黏度、流變減黏性、形成方法、形成條件等因素來決定爲 適合的大小，具體而言，當將橫向剖面置換或近似於圓形 時，較佳係調整爲直徑200nm~1 000 " m，尤佳爲直徑 20〇nm〜l〇〇〇nm的大小之間。此外，點之間的距離並無特 別限定，較佳爲〇〜點直徑的約1/2，尤佳爲距離爲0，亦即 於點之間無間隙。 細微凹凸構造可形成爲1個或2個以上的任意數，但爲 了提高聚光效果，較佳係調整爲預定數目。具體而言，每 1平方吋較佳爲1〜2.5X109個，尤佳爲1χ1〇8〜2.5X109個。凹 凸（凸部）可呈規則地配列，或是不規則地配置。此外， 當凹凸呈規則地配置時，可爲方格狀的配置或蜂巢狀的配 置。 形成有本發明之光電動勢裝置用保護基板的透明基板 ’只要是具有預定的強度與光穿透率，可形成後述的細微 -17- 201133901 凹凸構造，且具有可保護太陽能電池單元等的光發電裝置 之功能者，則可爲玻璃材、樹脂材料或其他材料，並無特 別限定。透明基板，較佳者係相對於4 0 〇〜1 1 0 0 n m的全波長 之光穿透率’以積分値（加權平均）計爲80%以上，特佳 爲90%以上。或是就發電裝置的特性上，主要有益於發電 之波長區段具有前述光穿透率者。 透明基板用的玻璃材並無特別限制，可從一般所用之 納耗一氧化砂玻璃中選擇出滿足要求的特性者，此般玻璃 ’市售品中亦具有適用各種用途之種種特性的玻璃。此外 ，因情況的不同，亦可使用二氧化矽玻璃、硼矽酸玻璃等 之其他組成系的玻璃》 透明基板用的樹脂材料，例如可列舉出丙烯酸、聚碳 酸酯、聚苯乙烯、氯乙烯、聚對苯二甲酸乙二酯等。此外 ，如後述般’亦可與細微凹凸構造形成用樹脂爲同一材料 〇 本發明之細微凹凸構造係由透明的樹脂材料所形成， 且其光穿透率與上述基板相同。樹脂材料的折射率，較佳 爲玻璃的折射率以下。具體而言，折射率η在波長589.3nm 的D線中爲1.50以下，尤佳爲1.45以下，更佳爲1.42以下， 特佳爲1.4〇以下。當折射率低時，與空氣之界面上的反射 降低，使入射光增加而能夠提升光電轉換效率。 樹脂材料並無特別限定，只要是具有預定的強度與光 穿透率，可形成細微凹凸構造，且具有可保護太陽能電池 單元等之功能者均可使用任一樹脂。例如可列舉出丙烯酸 -18- 201133901 樹脂、環氧樹脂' PC (聚碳酸酯）、TAC(三乙酸纖維素 )、PET (聚對苯二甲酸乙二酯）、PVA (聚乙烯醇）、 PVB (聚乙烯丁醛）、PEI (聚醚醯亞胺）、聚酯' EVA ( 乙烯-乙酸乙烯指共聚物）、PCV (聚氯乙烯）、PI (聚酿 亞胺）、PA (聚醯胺）、PU (聚胺基甲酸酯）、PE (聚 乙烯）、PP (聚丙烯）、PS (聚苯乙烯）、PAN(聚丙稀 腈）、丁醛樹脂、ABS (丙烯腈-丁二烯-苯乙烯共聚物） 、ETFE (乙烯-四氟乙烯共聚物）、PVF (聚氟乙烯）等 之氟樹脂、聚矽氧樹脂、或是賦予此等樹脂熱硬化性或紫 外線等之活性能量線硬化性之樹脂組成物。 此外’考量到製造、加工的容易性等，較佳爲紫外線 等之活性能量線硬化性樹脂或是熱硬化性樹脂。 活性能量線硬化型樹脂，較佳爲紫外線硬化型樹脂， 可列舉出聚矽氧樹脂、丙烯酸樹脂、不飽和聚酯樹脂、環 氧樹脂、環氧丙烷樹脂及聚乙烯醚樹脂等，此等可使用1 種或2種以上’更佳爲將此等進行氟化後之樹脂。 熱硬化型樹脂’例如可列舉出環氧樹脂、三聚氰胺樹 脂、脲樹脂、胺基甲酸酯樹脂、及聚醯亞胺樹脂，或是矽 氮院及聚砂氧樹脂等之無機系聚合物等，此等可使用1種 或2種以上，更佳爲將此等進行氟化後者。 此外，本發明中亦可使用熱可塑性樹脂。熱可塑性樹 脂中’較佳爲含有氟之熱可塑性樹脂。含氟的熱可塑性樹 脂’例如可列舉出ETFE、住友3M公司製的THV、Arkema 公司製的Kynar般之脂肪族系氟樹脂或DuPont公司製的 -19 - 201133901[Technical Field] The present invention relates to a protective substrate for a photovoltaic device and a method for manufacturing the same, in particular, a protective substrate for a photoelectromotive force device having a small light-receiving efficiency Production method. [Prior Art] A photoelectromotive force device that generates an electromotive force when exposed to light is used as an alternative energy source for solving environmental problems of existing power generation methods such as thermal power plants, hydroelectric power plants, nuclear power plants, and the like. Solar power generation systems, etc. This solar power generation system, generally referred to as a solar battery, is one of the biggest problems of current solar cells, which is a problem of low power generation efficiency. Regarding the method for improving power generation efficiency, various techniques have been explored in the past, but mainly focused on improving the light/electric conversion efficiency (photoelectric conversion efficiency) of the solar cell itself. In order to protect the unit, the solar cell module has a surface protection member of a glass or a transparent resin film on the surface of the unit. However, in this part, the countermeasure for improving the power generation efficiency can be said to be uncompleted. Usually, no treatment is applied to this transparent protective member. When a solar cell module using such a general protective member is, for example, a glass substrate, sunlight of about 3-4% is reflected on the surface. This reflected light is completely unhelpful for power generation, and is therefore a major factor in reducing the power generation efficiency of the solar cell module. Japanese Laid-Open Patent Publication No. Hei 9-1 9 1 1 1 (Patent Document 1) discloses the following solar cell module, that is, a fibrous inorganic compound impregnated with irregularities of a predetermined size of -5 to 201133901. A transparent organic polymer resin (EVA or the like) is disposed on the light incident side of the photoelectromotive force element, thereby preventing the reflected light from reaching other houses or the ground and causing the person located there to feel glare and uncomfortable, so that the transparent organic polymer resin The collapse of the solar cell module is not conspicuous, prevents dirt from adhering to the surface, and can withstand outdoor use for a long period of time. However, the concavo-convex structure of this document aims to prevent the above-mentioned glare and dirt from being attached, and has not been discussed for preventing surface reflection in order to improve power generation efficiency. Further, in this document, in order to provide irregularities on the surface of the covering material, the fibrous inorganic compound is impregnated with the transparent organic polymer resin, but specifically, a glass fiber nonwoven fabric, a glass fiber woven fabric, a glass enamel filler or the like is used. However, it is necessary to have a procedure for dispersing such fibers in a resin, and it is also necessary to strictly manage the degree of dispersion within the evaluation range, which is not only accompanied by difficulties in mass production procedures, but also increases in manufacturing costs. Further, in the case of long-term use, the fiber also needs to be subjected to an underlayer treatment for ensuring sufficient adhesion with the resin material, which also becomes a factor of an increase in steps. In Japanese Laid-Open Patent Publication No. 2008-260654 (Patent Document 2), the following method is disclosed, that is, a film layer having a high refractive index and a low refractive index is used and laminated on both sides of the cover glass or only on the surface. In this way, the method of suppressing the reflection of the wavelength region of the photoelectric conversion by the solar cell unit is suppressed, thereby increasing the amount of light penetration. However, in the technique of this document, the reflection suppressing effect is obtained by a combination of film layers having different refractive indices, so that it is not expected to suppress the light which is reflected at the surface -6 - 201133901 itself or relative to the incident angle. Small light improvement effect. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2008-260654 (Patent Document 2) (Problems to be Solved by the Invention) Problems to be Solved The point is to provide a protective substrate for a photovoltaic device that is easy to manufacture and that can improve the light collecting efficiency, and that is most suitable for a photovoltaic device having a photoelectric conversion efficiency higher than that of the conventional structure, and a method for manufacturing the same. (Means for Solving the Problem) A glass or a transparent resin film used for protection of a solar cell unit has a refractive index of 1,500 or more and has a large refractive index difference from the atmosphere (air), so that it has a surface. The problem of large refractive index. The relationship between the incident angle of light and the reflectance of the glass surface when the refractive index of air is 1.00 and the refractive index of glass is 1.52 is as shown in the following table. The angle of refraction in the table is the angle at which the normal direction of the glass plane is taken as the incident angle of 0 degrees. 201133901 [Table 1] (.2__0 15 30 45 60 75 90 Reflectance (%) 4.3 4.7 6.1 9.7 18 41 〇 From the first table, it can be known that even if it is glass, even vertical incidence (〇) More than 4% of the light produces reflections. In addition, the obliquely incident light has a larger reflection 'for example, when the incident angle is 70 degrees, the reflectivity is 30% or more. Therefore, especially for oblique incidence on the surface of the substrate. In order to solve the problem, the present invention has the following configuration. (1) A protective substrate for a photovoltaic device having a concave-convex structure on a surface of a transparent substrate disposed on a photosensitive portion (2) The protective substrate for a photovoltaic device according to the above (1), wherein the transparent substrate is formed of glass. The transparent resin layer has a refractive index of the transparent substrate. (3) The protective substrate for a photovoltaic device according to (1) or (2) above, wherein the transparent resin layer is formed of a resin, a resin, and an inorganic material. (4) As in the above (1) to (3) One light electric In the protective device substrate, the area of the portion where the tangent to the convex portion surface constituting the uneven structure and the normal line with respect to the substrate surface is 60 degrees or less is 5% or more of the entire uneven structure area. The protective substrate of the photoelectromotive force device -8 - 201133901, wherein the cross-sectional shape of the concave-convex structure in the normal direction of the transparent substrate is a shape or approximate to a part of a circle. In the shape of a triangle, the size of the bottom surface of these is 2〇〇nm, ΙΟΟΟμηι, and the number of convex portions is 1~2.5χ109 per 1 square centimeter. (6) As above (1)~( (5) The protective substrate for a photoelectromotive force device according to any one of the above (1) to (5), wherein The transparent resin layer has a heat or a photocurable resin. (8) A method for producing a protective substrate for a photovoltaic device, wherein a transparent resin having a refractive index equal to or lower than a transparent substrate is laminated on a transparent portion disposed in the photosensitive portion On the plate, fine irregularities are formed on the surface of the transparent resin layer, and the transparent resin layer is cured at any stage during or after formation, and a fine uneven structure is formed on the surface of the transparent resin layer. The method for producing a protective substrate for a photovoltaic device according to the above (8), wherein a mold having a fine unevenness or a linear member is combined to press the surface of the transparent resin layer or a rigid body having protrusions or hooks. (10) The method for producing a protective substrate for a photovoltaic device according to the above (8), wherein the transparent resin is laminated, by a photomask method or The photoforming method is formed into irregularities. (11) A method of producing a protective substrate for a photovoltaic device according to the above (8), wherein the transparent resin is laminated to a fine concave pattern by a printing method to form irregularities. (12) The method for producing a protective substrate for a photovoltaic device according to the above (8), wherein the resin material is applied onto a transparent substrate to form a fine uneven structure. (13) A method of producing a protective substrate for a photovoltaic device according to the above (12), wherein the coating is performed by a dispenser or an inkjet. (14) The method for producing a protective substrate for a photovoltaic device according to any one of the above (8), wherein the transparent resin layer has a heat or photohardenable resin (15) as described above (8) to (14) The method for manufacturing a protective substrate for a photoelectromotive force device according to any one of the present invention, wherein the shape of the convex portion constituting the fine uneven structure is approximate to a shape of a part of the cut ball, and the radius of curvature A of the convex portion and the cut surface The relationship of the radius B of the approximate circle of the cut surface is expressed by the following formula (1), B ^ A/2 ( 1 ). Advantageous Effects of Invention According to the present invention, since the transparent resin has a low refractive index, the reflectance can be more reduced than that of a polymer film such as glass or PET. In addition, since a three-dimensional fine concavo-convex texture structure is formed, it is possible to reduce the reflectance, and to provide a protective substrate for a photovoltaic device which is most suitable for a photovoltaic device having a higher photoelectric conversion efficiency than that of the prior art, and a method for manufacturing the same. Further, according to the method for manufacturing a protective substrate for a photovoltaic device according to the present invention, the fine uneven structure can be continuously manufactured with a simple configuration and at a low cost, and the protective substrate for a photovoltaic device can be manufactured in the mass production step. It is extremely useful. [Embodiment] The protective substrate for a photovoltaic device according to the present invention is provided on a surface of a transparent substrate disposed on a photosensitive portion of a photoelectric potential device, and is provided with a transparent resin layer having fine irregularities. Hereinafter, an embodiment of the present invention will be described with reference to the drawings. Fig. 1 is a view showing an example of a configuration of a protective substrate for a photovoltaic device according to the present invention. In the first embodiment, the protective substrate for a photovoltaic device includes a transparent substrate 1 〇 1 and a fine uneven texture structure 102 composed of a transparent resin formed on a transparent substrate. Fig. 2 is a view showing another example of the configuration of a protective substrate for a photovoltaic device according to the present invention. In the second embodiment, the protective substrate for a photovoltaic device includes a transparent substrate 200 and a transparent resin layer 202 having a fine uneven texture structure made of a transparent resin formed on a transparent substrate. As shown in Fig. 4, the concavo-convex structure may be a shape similar to a part of the ball. Figs. 3 and 4 are schematic views showing third and fourth configuration examples of the protective substrate for a photovoltaic device according to the present invention. In the third embodiment, the protective substrate for a photovoltaic device includes a transparent substrate 301 and a fine uneven structure 302 formed on the transparent substrate. In addition, in the fourth embodiment, the protective substrate for a photovoltaic device includes a transparent substrate 401 and a fine concavo-convex structure layer 402 having a fine concavo-convex structure formed on the transparent substrate, and a fine concavo-convex texture structure formed on the transparent substrate. As in the example of FIG. 1 and -11 - 201133901, FIG. 3, the fine concavo-convex structure 302 may be directly formed on the upper portion of the transparent resin layer, and the concavo-convex structure may be an independent structure, or as shown in FIG. 2 and FIG. In the example of the figure, a transparent resin layer having a fine uneven structure is disposed on a substrate, and a fine uneven texture is formed on the upper portions of the transparent resin layers 202 and 402. Next, the principle of the present invention will be described. Fig. 6 and Fig. 7 are schematic views showing a protective substrate for a photovoltaic device according to the principle of the present invention. In the fine concavo-convex structure of the present invention, the cross-sectional shape of the convex portion formed is a shape approximate to a part of a circle or a shape similar to a triangle. Therefore, the longitudinal section and the transverse section are quadrangular except for the square. In Fig. 6, the fine uneven structure 2 of the present invention is formed on the substrate 1. This fine concavo-convex structure is formed into a triangular shape in this example for ease of explanation. First, the case where the light beams L1, L2, and L3 are irradiated onto the substrate from the vertical direction will be discussed. When the light rays L1, L2, and L3 reach the slope of the fine concavo-convex structure 2, a part thereof penetrates and the other portions reflect. The reflectance at this time was set to 4%. Here, when focusing on the light ray L2, the transmitted light 12 is the amount of the incident light L2 minus the reflected light L2', and when incident on the fine uneven structure 2, the incident angle Δn is incident due to the refractive index η of the material. And penetrate the substrate 1 and reach the unit not shown in the figure. On the other hand, each of the reflected lights LI', L2', and L3' is incident on another fine structure, and some of the reflected light L1 ", L2", L3 " are diffused to the outside and are scattered. Here, incident on other subtle The incident light 1 Γ of the reflected light L 1 " is structured to be incident by the refractive index 0 η and then reflected at the other interface, so that the incident light 1 Γ ' penetrates the substrate and reaches the cell. As described in the above-mentioned -12-201133901, a part of the incident light, although not shown in the drawing, diffuses to the outside at the aforementioned interface. The other reflected lights L2', L3' are also the same, incident on other fine structures, and a part of them reach the cell. Thus, by providing a fine structure on the surface of the substrate, a part of the reflected light which has been diffused to the outside and is lost to the present can be introduced and guided to the unit, which is advantageous for photoelectric conversion efficiency and improves power generation efficiency. In this example, the structure in which the 0 t is a 45° cross-sectional triangle is explained for ease of explanation. However, when the incident angle of the light is 45°, it is difficult to obtain an efficiency improvement effect by the above configuration. Therefore, when the profile is triangular, it is necessary to consider setting the environment and the like to design an optimum angle. Next, a case of a hemispherical fine concavo-convex structure will be described with reference to Fig. 7. In the figure, the fine uneven structure 2 of the present invention is formed on the substrate 1. In this example, the fine concavo-convex structure is formed in a hemispherical shape so as to be in contact with each convex portion. It is first assumed that the light rays L1, L2, L3 are irradiated onto the substrate 1 from the vertical direction. When the light beams L1, L2, and L3 reach the curved surface of the fine concavo-convex structure 2, the same portion as described above penetrates, and the other portions are reflected. Here, the tangent to the angle 0 t of the fine concavo-convex structure 2 with respect to the normal line of the substrate surface is set to t of 60 degrees, and the intersection with the convex curve is p. When focusing on the light ray L 1 incident from the point P at a region where the tangential line and the normal line are smaller, the transmitted light 1 1 is the amount of the reflected light L j subtracted from the incident light L 1 'when incident on In the fine concavo-convex structure 2, the refractive index η' of the material is incident at an angle θη and penetrates the substrate 1 to reach a unit not shown in the drawing. On the other hand, the reflected light L1 is incident again on the adjacent fine concave -13 - 201133901 convex structure, and as described above, after deducting the reflected light, it is biased toward 0 η and penetrates the substrate 1 to reach the cell. The transmitted light 11, 12, 13 incident on the spherical surface is deflected in such a manner as to converge on a specific focus. Then, attention is paid to the light ray L2 which is incident on the region where the angle between the tangential line and the normal line is large, and the transmitted light L2 of the reflected light L2' is subtracted from the incident light L2, and when incident on the fine uneven structure 2, Due to the refractive index η of the material, the deflection angle 0 η is incident and penetrates the substrate 1 and reaches a unit not shown in the drawing. On the other hand, since the reflected light L2' is reflected toward the upper angle, it is not incident on the adjacent fine concavo-convex structure again and is lost. In this example, light from a direction perpendicular to the surface of the substrate is considered, but in a light obliquely incident on the surface of the substrate, even if the angle formed by the point Ρ from the tangent to the normal is large, It is also possible to enter the concave and convex structure again. However, compared with the region where the angle incident on the tangent and the normal is smaller, the probability that the reflected light is not incident again and is lost in a larger region is higher. As described above, even if the fine concavo-convex structure of the curved surface is formed, a part of the reflected light can be re-incident and effectively utilized. Further, compared with the unevenness of the triangle, the surface parallel or perpendicular to the various incident lights is extremely small, and the change in efficiency caused by the incident light is small. The shape of the fine uneven texture is not limited to a geometric structure such as a quadrangular pyramid or a cone or a hemisphere, and may be formed into various shapes such as a cylindrical shape or a polygonal column type. In addition, the oblique incident angle can be lowered by having a vertical plane or a slope to enhance the concentrating efficiency. Therefore, in the present invention, in particular, the shape of the concavo-convex structure may be formed such that the cross section in the normal direction of the substrate surface approximates a part of a circle or the cross section approximates a triangular shape. That is, the shape of the -14-201133901 ′ is a shape of a part of the cut ball or a shape similar to a conical shape. These shapes are easy to form and are advantageous in terms of the manufacturing process. In the present invention, when the angle of the slope of the uneven structure is formed, the angle of the substrate in the normal direction is 0, and the angle of inclination is 60 degrees or less. The portion of the light reflected by the slope will reach the other slope and become refracted light, making the light act more effectively. Therefore, the surface ′ of the convex portion constituting the fine concavo-convex structure preferably has a portion at which the angle between the tangential line and the normal line with respect to the substrate surface is 60 degrees or less. Specifically, the area of the portion which is 60 degrees or less is 5% or more of all the fine concavo-convex structure areas, more preferably 2% or more, and particularly preferably 30% or more. When it is set to 5% or more, it is expected that an increase in the amount of incident light of about 2% can be expected to be obtained when considering a trapezoidal structure having a trapezoidal shape having a full area of 2.5% of the inclined portions at both ends. The gain boost effect. Further, when the shape of the convex portion of the fine uneven structure is approximately hemispherical, the upper limit 前述 of the aforementioned area is about 50%. The tangent to the surface constituting the convex portion is, for example, as shown in Fig. 8. When the hemispherical convex portion is considered, the cross-sectional shape 2' of the hemisphere is semicircular. The tangent lines P 1 and P 2 with respect to the semicircle are tangent to the surface constituting the convex portion, and are tangent to the cross section of the convex portion. Further, the angle formed by the normal line P0 with respect to the surface of the substrate and the tangent is the above angle. This angle is the angle on the acute angle side among the angles formed by the normal line p 〇 and the aforementioned tangent line. Further, these are judged not to have the same cross section as the cross section of the convex portion. The shape of the convex portion constituting the fine concavo-convex structure of the present invention can be formed into a shape in which the cross section approximates a part of a circle, that is, a shape similar to a portion of the cut ball -15-201133901. Usually, the formed convex portion is not close to a true spherical shape, and is mostly a spherical shape after deformation, but it is difficult to directly evaluate such a shape. Therefore, when evaluating the convex portion, the system is considered to be similar to a part of the ball. The approximate technique ' can be replaced by a part of a circular shape of the equivalent area by image analysis or the like, or replaced by a part of a circle having the most approximate shape. Further, the same is true when the cross section of the triangular pyramid or the like is approximated to the shape of a triangle. The relationship between the radius of curvature A of the convex portion which approximates a part of the ball and the radius B of the approximate circle of the cut section after cutting is expressed by the following formula (1). B ^ A/2 ( 1 ) The radius of curvature A of the convex portion is a radius of curvature of a sectional shape of a convex portion which approximates a part of the ball as described above. Further, the approximate circle of the cut section after the cutting is a shape of the cut portion when the convex portion is approximated to the shape of a part of the cut ball, and since this portion is also approximate to a circle, it is defined as an approximate circle. The radius B of the approximate circle is preferably 1/2 or more of the radius of curvature A, that is, the relationship of the above formula is satisfied. For example, as shown in Fig. 9, when the convex portion is hemispherical, the cross section is semicircular. The radius of curvature of this semicircle is equal to the radius B 1 of the approximate circle which is the cut surface of the base of the convex portion, and becomes B = A. However, even with a spherical shape having the same curvature radius, as the cut portion becomes smaller, the radius of the approximate circle of the cut surface becomes smaller B2, B3, B4. The radius B4 of the approximate circle of the cut surface is exactly 1/2 of the radius of curvature A. When the radius B 5 of the approximate circle which is the smaller cut surface is smaller, the cut spherical shape becomes extremely small, and the effect as a fine uneven structure cannot be expected too much. Therefore, as long as the relationship of the above formula is satisfied, the radius B5 of the approximate circle of the cut surface is defined as 1/2 -16 to 201133901 or more of the radius of curvature A. Further, it is preferably B g 2A/3, particularly preferably B 2 3A/4, and particularly preferably B 2 4A/5. The closer the shape of the convex portion is to the hemispherical shape, the easier it is to obtain an efficiency improvement effect. On the other hand, when the size of B is closer to A to some extent, even if it is further approximated, the improvement effect cannot be expected too much. The size of the fine concavo-convex structure is not particularly limited. However, when the average height of the height is 2 mm or more, there is a fear that light is incident due to oblique incident light. In addition, individual sizes may have variations. Further, when the size of the fine uneven texture is equal to or less than the wavelength of light, the refractive index continuously changes in the thickness direction, and an optical effect in which the interface having the refractive index difference is eliminated can be exhibited. The size of each convex portion (dot) is not particularly limited, and may be determined to be a suitable size depending on factors such as viscosity of the resin, rheological viscosity reduction, formation method, and formation conditions, and specifically, when the transverse profile is replaced or approximated In the case of a circle, it is preferably adjusted to a diameter of 200 nm to 1 000 " m, and more preferably between 20 〇 nm and 1 直径 nm in diameter. Further, the distance between the dots is not particularly limited, and is preferably about 1/2 of the diameter of the 〇 to dot, and particularly preferably the distance is 0, that is, there is no gap between the dots. The fine concavo-convex structure may be formed in any number of one or two or more, but in order to enhance the condensing effect, it is preferably adjusted to a predetermined number. Specifically, it is preferably 1 to 2.5 x 109 per 1 square inch, and particularly preferably 1 to 1 to 8 to 2.5 x 109. The concave projections (protrusions) may be arranged regularly or irregularly. Further, when the irregularities are regularly arranged, they may be in a checkered configuration or a honeycomb configuration. The transparent substrate ′ having the protective substrate for a photovoltaic device according to the present invention has a predetermined intensity and light transmittance, and can form a fine -17-201133901 concave-convex structure to be described later, and has photovoltaic power generation capable of protecting solar cells and the like. The function of the device may be glass material, resin material or other materials, and is not particularly limited. The transparent substrate is preferably 80% or more, more preferably 90% or more, in terms of integral enthalpy (weighted average) with respect to a light transmittance of a full wavelength of 40 〇 to 1 1 0 0 n m. Or in terms of the characteristics of the power generating device, the wavelength section mainly contributing to power generation has the aforementioned light transmittance. The glass material for the transparent substrate is not particularly limited, and those which satisfy the required characteristics can be selected from the general consumption of the sulphur oxide glass. The glass s commercially available product also has various properties suitable for various uses. In addition, depending on the case, a resin material for a transparent substrate such as glass of other components such as cerium oxide glass or borosilicate glass may be used, and examples thereof include acrylic acid, polycarbonate, polystyrene, and vinyl chloride. , polyethylene terephthalate, and the like. Further, as described later, the resin may be the same material as the resin for forming a fine uneven structure. The fine uneven structure of the present invention is formed of a transparent resin material, and the light transmittance thereof is the same as that of the above substrate. The refractive index of the resin material is preferably equal to or lower than the refractive index of the glass. Specifically, the refractive index η is 1.50 or less in the D line having a wavelength of 589.3 nm, more preferably 1.45 or less, still more preferably 1.42 or less, and particularly preferably 1.4 Å or less. When the refractive index is low, the reflection at the interface with air is lowered, and the incident light is increased to increase the photoelectric conversion efficiency. The resin material is not particularly limited as long as it has a predetermined strength and light transmittance, and can form a fine uneven structure, and any resin having a function of protecting a solar cell unit or the like can be used. For example, acrylic acid-18-201133901 resin, epoxy resin 'PC (polycarbonate), TAC (cellulose triacetate), PET (polyethylene terephthalate), PVA (polyvinyl alcohol), PVB (polyvinyl butyral), PEI (polyether phthalimide), polyester ' EVA (ethylene-vinyl acetate copolymer), PCV (polyvinyl chloride), PI (polyimide), PA (polyamide) ), PU (polyurethane), PE (polyethylene), PP (polypropylene), PS (polystyrene), PAN (polyacrylonitrile), butyral resin, ABS (acrylonitrile-butadiene) -styrene copolymer), fluorocarbon resin such as ETFE (ethylene-tetrafluoroethylene copolymer) or PVF (polyvinyl fluoride), polyoxyxylene resin, or active energy ray for imparting thermosetting or ultraviolet rays to these resins A hardenable resin composition. Further, it is preferably an active energy ray-curable resin such as ultraviolet rays or a thermosetting resin, in view of ease of production and processing. The active energy ray-curable resin is preferably an ultraviolet curable resin, and examples thereof include a polyoxyxylene resin, an acrylic resin, an unsaturated polyester resin, an epoxy resin, a propylene oxide resin, and a polyvinyl ether resin. One or two or more types of resins which are more preferably fluorinated. Examples of the thermosetting resin are, for example, an epoxy resin, a melamine resin, a urea resin, a urethane resin, and a polyimide resin, or an inorganic polymer such as a ruthenium furnace or a polysiloxane resin. These may be used alone or in combination of two or more, and it is more preferred to fluorinate the latter. Further, a thermoplastic resin can also be used in the present invention. The thermoplastic resin is preferably a thermoplastic resin containing fluorine. For example, ETFE, THV manufactured by Sumitomo 3M Co., Ltd., Kynar-like aliphatic fluororesin manufactured by Arkema Co., Ltd., or DuPont Co., Ltd. -19 - 201133901

Teflon (註冊商標）AF、旭硝子公司製的Cytop般之脂環 式氟樹脂。 再者，前述活性能量線聚合型的丙烯酸樹脂，較佳爲 含有氟基者。藉由使丙烯酸樹脂含有氟基，可容易地降低 折射率。此外，藉由進行氟化，可提高撥水性，使防污功 能提高，並防止光電轉換效率隨時間經過而產生劣化者。 丙烯酸樹脂，較佳爲丙烯酸或甲基丙烯酸聚合物或共 聚物。此般聚合物，可列舉出聚甲基丙烯酸甲酯、聚丙烯 酸正丁酯、聚丙烯酸三級丁酯、聚甲基丙烯酸三級丁酯、 聚甲基丙烯酸十八烷酯、聚甲基丙烯酸三氟乙酯、聚甲基 丙烯酸環己酯、聚甲基丙烯酸苯酯、聚甲基丙烯酸縮水甘 油酯及聚甲基丙烯酸烯丙酯等。 此外，形成聚合物或共聚物之較佳單體，例如可列舉 出甲基丙烯酸甲酯、丙烯酸甲酯、甲基丙烯酸乙酯、丙烯 酸乙酯、甲基丙烯酸丙酯、丙烯酸丙酯、甲基丙烯酸丁酯 、丙烯酸丁酯、甲基丙烯酸縮水甘油酯、丙烯酸縮水甘油 酯、甲基丙烯酸甲氧乙酯、丙烯酸甲氧乙酯、甲基丙烯酸 丙酮酯、甲基丙烯酸丁酮酯、丙烯酸戊酯等。 較佳的氟化單體，例如可列舉出丙烯酸三氟乙酯、甲 基丙烯酸三氟乙酯、丙烯酸四氟丙酯、甲基丙烯酸四氟丙 酯、丙烯酸六氟異丙酯、甲基丙烯酸六氟異丙酯、甲基丙 烯酸六氟丁酯、丙稀，酸七氟丁酯、甲基丙烯酸五氟丙酯、 丙烯酸五氟丙酯等。 較佳的氟化丙烯酸樹脂，例如可列舉出聚（丙烯酸 -20- 201133901 1,1，1，3,3,3-六氟異丙酯）n=l_3 75、Tg = -23 ' 聚（丙烯酸 2,2,3,3,4,4,4-七氟丁酯）1^=1.377、丁§ = -30、聚（甲基丙烯 酸 2,2,3,3,4,4,4-七氟 丁酯）n= 1.383、Tg = 6.5、聚（丙烯酸 2,2,3,3,3-五氛丙醋）11=1_389、丁§ = -26、聚（甲基丙稀酸 1，1，1，3,3,3 -六氟異丙酯）n=l_39、Tg = 56、聚（丙烯酸 2,2,3,4,4,4 -六氟 丁酯）n = 1.394、Tg = -22、聚（甲基丙烯 酸2,2,3,4,4,4-六氟丁酯）、聚（甲基丙烯酸2,2,3,3,3-五氟 丙酯）n=1.395、Tg = 70、聚（丙烯酸2,2,2 -三氟乙酯） n=1.411、Tg = -i〇、聚（丙烯酸 2,2,3,3-四氟丙酯）η = 1·415 、丁§ = -22、聚（甲基丙烯酸2,2,3,3-四氟丙酯）11=1.417、 丁呂=68、聚（甲基丙烯酸2,2,2-三氟乙酯）11=1.418'丁8=69 等。此等樹脂，其折射率η爲1.42以下’尤其爲1·4〇以下’ 故可期待低折射率所帶來之表面反射率的降低效果。 聚合物的數量平均分子量，通常約爲5〇〇〇〜500000g/ 莫耳，聚合物的重量平均分子量約爲1 0000〜1 000000。 爲了獲得上述樹脂材料，例如可藉由一般所知的方法 將例示的單體等進行聚合硬化並形成聚合物而藉此製得。 具體而言，可列舉出預先將藉由加熱以產生自由基之熱聚 合起始劑添加於單體組成物，然後進行加熱來進行聚合之 方法（以下有稱爲「熱聚合」時），以及預先將藉由紫外 線等之活性能量線以產生自由基之光聚合起始劑添加於單 體組成物’然後照射活性能量線來進行聚合之方法（以下 有稱爲「光聚合」時）等，以及預先添加自由基聚合起始 劑來進行聚合之方法’本發明中，尤佳爲光聚合。 -21 - 201133901 此外’爲了容易形成凸部的形狀，添加流變減黏性賦 予劑者亦爲有效的方法。流變減黏性賦予劑，只要是表面 積大的無機系微粒即可，例如以此般目的所添加之微粒粉 ’較佳爲藉由氣相反應所合成之無機微粒，例如可列舉出 發煙二氧化矽（fumed silica )、發煙二氧化矽鋁、發煙二 氧化鈦等。具體而言，可使用二氧化矽鋁（Aerosil MOX170)、氧化鋁（Aerooxide Alu C)或是二氧化鈦（ Aerooxide Ti02 P25)或是二氧化銷（Sumitomo Osaka Cement公司製的OZC-8YC或是Tosoh公司製的TZ-8Y)等， 此等可使用1種或2種以上，該添加量爲任意量，一般是以 相對於原料樹脂總量而言爲0.1〜10質量％的範圍來添加。 原料組成物中，除了上述流變減黏性賦予劑之外，亦 可含有各種副成分。副成分可列舉出可進行自由基聚合之 其他單體、抗氧化劑、紫外線吸收劑、紫外線安定劑、染 顏料、塡充劑、矽烷偶合劑、禁聚合劑、光安定劑等之添 加劑。該添加量爲任意量，可在不會對構成樹脂之主成分 造成不良影響之範圍內，因應必要來添加。 形成透明樹脂層時，例如可藉由一般所知的方法將含 有例示的單體、聚合物等之組成物進行聚合硬化並形成聚 合物、共聚物而藉此製得。具體而言，可列舉出預先將藉 由加熱以產生自由基之熱聚合起始劑添加於單體組成物， 然後進行加熱來進行聚合之方法（以下有稱爲「熱聚合」 時），以及預先將藉由紫外線等之活性能量線以產生自由 基之光聚合起始劑添加於聚合性組成物，然後照射活性能 -22- 201133901 量線來進行聚合之方法（以下有稱爲「光聚合」時）等， 以及預先添加自由基聚合起始劑來進行聚合之方法，本發 明中，尤佳爲光聚合。 熱聚合起始劑’例如可列舉出過氧化氫、過氧化苯甲 醯（苯甲醯過氧化物）、二異丙基過氧碳酸酯、三級丁基 過氧基（己酸2-乙酯）、2,2·-偶氮雙異丁腈、4,4'-偶氮雙 (環己腈）、4,4'-偶氮雙（4-氰基戊酸）及2,2，-偶氮雙（ 2 -甲基丙烷）等之偶氮化合物等。如亦爲有機過氧化物之 Trigonox 21及Perkadox 16般之其他市售製品，亦可用作 爲起始劑。 上述熱聚合起始劑可單獨使用或倂用2種以上。熱聚 合起始劑的添加量，相對於單體總計而言，通常爲 0，0 1〜2 0質量％。 此外，光聚合起始劑，例如可列舉出二苯基酮、安息 香乙醚、安息香丙醚、二乙氧苯乙酮、1-羥基環己基苯酮 、2,6-二甲基苯甲醯基二苯基膦氧化物、2,4,6-三甲基苯甲 醯基二苯基膦氧化物、2-羥基- l-{4-[4-(2-羥基-2-甲基-丙醯基）-苯甲基]苯基}-2-甲基-丙烷-卜酮、苯甲基二甲基 縮酮、4- ( 2-羥基乙氧基）苯基-(2-羥基-2-丙基）酮、2-甲基-2-嗎啉基（4-硫甲基苯基）丙烷-1·酮等。尤其只要 是自由基系光聚合起始劑，則無特別限定’較佳爲羥基-卜{4-[4-(2-羥基-2-甲基-丙醯基）-苯甲基]苯基}_2-甲基-丙烷-1 -酮（商品名稱：Irgacure 127 )等。此外’調配後 其貯藏安定性需佳。 -23- 201133901 上述光聚合起始劑可單獨使用或倂用2種以上。光聚 合起始劑的添加量，相對於單體總計而言，通常爲 0.01〜10質量％。當光聚合起始劑的添加量過多時，聚合急 遽地進行，在光學特性、強度等方面可能會造成不良影響 。另一方面，若過少時，原料組成物會有無法充分聚合之 疑慮。 所照射之活性能量線的量，只要在光聚合起始劑可產 生自由基之範圍內即可，可爲任意量，但在極少量時，聚 合不完全，無法充分顯現硬化物的耐熱性、機械特性，相 反的，當極度過剩時，會產生硬化物的黃變等之光所導致 的劣化，所以可配合單體的組成以及光聚合起始劑的種類 、量，較佳例如在0.1〜200J/cm2的範圍內照射200~400nm 的紫外線。尤佳爲分割成複數次來照射活性能量線。亦即 ’第1次照射全部照射量的1 /20〜1 /3，第2次以後再照射所 需剩餘量，如此可得複折射率更小之硬化物。照射時間， 可因應樹脂量與硬化程度來適當的調整。通常在1秒~1〇分 鐘間進行調整。 所使用之光源，可使用紫外線LED、藍色LED、白色 LED等之LED (發光二極體）、氙氣燈、碳電弧、殺菌燈 、紫外線用螢光燈、定壓水銀燈、影印用高壓水銀燈、中 壓水銀燈、高壓水銀燈、超高壓水銀燈、無電極燈、鉈燈 、姻燈 '金屬 _化物燈、氣燈、Toshiba Harrison Lighting 公司製的準分子燈、F u s i ο η公司製的Η燈、Η P 1 u s燈、D燈 、V燈、Q燈、M燈等’或是太陽光，再者，亦可使用由掃 -24- 201133901 描型、幕型電子線加速路徑所形成之電子線等。此外、爲 了充分地進行硬化亦可在氮氣等之非活性環境中照射紫外 線等之活性能量線。 就迅速地完成聚合之目的下，可同時進行光聚合與熱 聚合。此時，與活性能量線照射的同時，可在3 0〜3 0 0 °C的 範圍內加熱聚合性組成物以進行硬化。此時，原料組成物 中，可添加用以完成聚合之熱聚合起始劑，但當大量地添 加時，如上述般有產生不良影響之疑慮，故此時的熱聚合 起始劑，相對於原料樹脂的總計而言，可在0 · 1〜2質量％的 範圍內使用。 原料組成物，可溶解於溶劑中使用。溶劑並無特別限 定，可因應必要來選擇最適者。具體而言，可使用醇及不 飽和醇等之醇系，或是有機系溶劑。 本發明中，可於前述基板與細微凹凸層之間形成底層 。藉由形成底層，可改善基板的潤濕性，提高與塗佈液之 接觸角，使塗佈液形成爲更接近半球之狀態。此外，亦可 期待改善與細微凹凸層之黏著性，以及改善無凹凸構造之 部分上的折射率之效果。此時，如第5圖所示，光電動勢 裝置用保護基板，係具有透明基板5 0 1以及形成於透明基 板上之底層503，然後於其上方形成有細微凹凸構造502。 底層並無特別限定，較佳爲接觸角較高的材料，具體 而言，相對於水之接觸角，必須爲一般玻璃的接觸角（3 0 °)以上，較佳爲60°以上，尤佳爲70°以上，特佳爲80°以 上。此般材料，例如可列舉出上述細微凹凸構造中所用之 -25- 201133901 樹脂材料，尤其是氟系樹脂，特別是氟系丙烯酸樹脂。此 材料在與細微凹凸構造之黏著性之觀點來看亦較佳，尤其 推薦使用與細微凹凸構造爲同一或同種的材料。 底層的膜厚並無特別限定，雖然愈薄愈佳，但可因應 形成方法或所使用之材料的特性、所要求之光學特性、耐 久性等’來調整爲最適膜厚。一般而言，就以潤濕性的改 善、黏著性的改善爲目的下，可約爲數l〇〇nm〜數1〇〇微米 ，該上限較佳約爲數毫米。 製造本發明之光電動勢裝置用保護基板時，可將折射 率與透明基板相同或以下之透明樹脂層合於配置在感光部 之透明基板上，將前述透.明樹脂層的表面成形爲細微的凹 凸’在形成中或形成後的任一階段中使前述透明樹脂層硬 化’而將細微的凹凸構造形成於此透明樹脂層的表面。具 體而言’係藉由塗佈法、塗層法、印刷法、浸漬法等將上 述硬化前的透明樹脂形成於透明基板的表面，來形成透明 樹脂層前驅物，然後將模具等之用以形成凹凸之構件按壓 於此前驅物予以成形，然後藉由預定的方法進行聚合·硬 化而形成透明樹脂層。 當藉由紫外線硬化型樹脂來形成透明樹脂時，首先藉 由塗佈等，將具有紫外線硬化型樹脂之透明樹脂材料層合 於透明基板的表面，來形成透明樹脂層前驅物。然後將具 有微細凹凸紋理的模具緊押於透明樹脂層前驅物，進行成 形，與此同時或之後照射紫外線使透明樹脂硬化。 用以形成細微凹凸構造之模具，並無特別限定，可使 -26- 201133901 用印刷法等所使用之模具、或是各種按壓模具。 狀可爲平板狀或是輥型式者，可構成爲適合製造 。此般模具，例如可將使Teflon (註冊商標）含 布並進行燒結所成之薄片，捲取於例如橡膠製等 成爲輥型式的模具來使用。 當使用此般輥型式的模具時，可藉由依據印 術來形成。具體而言，係將模具在形成有透明樹 物之透明基板上滾動，同時從透明基板的內面照 使透明樹脂硬化。或者是，將上述模具與紫外線 固定，並將層合有透明樹脂層前驅物之透明基板 等之間。 此外，亦可將具有複數個橫槽或凹凸之剛體 並旋轉來形成凹凸，或是以縱橫向來配置線狀、 金屬線、樹脂線並予以按壓來形成。再者，亦可 於剛性體之複數個鈎或突起來刮除或切削表面來 再者’在層合前述透明樹脂後，可藉由光罩 形法成形爲凹凸。亦即’當使用光罩法來成形時 硬化性的透明樹脂成膜後，將藉由依照欲形成的 之圖型的光罩予以覆蓋’然後照射光或輻射線等 使凸部的透明樹脂硬化。 此外’依據光成形法（photo molding)來成 使用掃描反射鏡或XY點繪器等裝置，—邊掃描 可見光雷射等之能量線一邊硬化。亦即，依照凹 能量線掃描照射在所成膜的樹脂表面，使凸$硬 模具的形 法之形狀 浸於玻璃 的輥而構 刷法之技 脂層前驅 射紫外線 產生手段 送入於此 予以按壓 絲狀的細 藉由形成 形成。 法或光成 ，在將光 凹凸形狀 之能量線 形時，係 紫外線或 凸形狀將 化來形成 -27- 201133901 凹凸。此外，亦可藉由照射紅外線雷射等之發熱性能量線 ，使用下列熱硬化性樹脂、熱可塑性樹脂來形成。 當藉由熱硬化性樹脂來形成透明樹脂層時，與上述相 同，於透明樹脂層前驅物形成細微的凹凸，然後與此同時 或之後進行加熱使透明樹脂硬化。 當使用熱硬化性樹脂時，可將捲繞在附有加熱器的金 屬輥之模具，在形成有透明樹脂層前驅物之透明基板上滾 動，並藉由使加熱器進行加熱來將熱賦予至熱硬化性樹脂 來進行熱硬化。或者是伴隨著模具的滾動，從透明基板側 照射紅外線，藉此將熱賦予至熱硬化性樹脂使其硬化。或 者是將上述模具或是上述模具與紅外線產生手段固定，並 將層合有透明樹脂層前驅物之透明基板送入於此等之間。 當藉由熱可塑性樹脂來形成透明樹脂層時，可將事前 經加熱使黏度降低之狀態的該樹脂塗佈於透明基板的表面 來形成透明樹脂層前驅物。或者是將透明樹脂溶解於溶劑 後，塗佈於透明基板上，然後使溶劑氣化而形成透明樹脂 層。 當使用熱可塑性樹脂時，與上述熱硬化性樹脂相同， 可將輥型式的模具在形成有透明樹脂層前驅物之透明基板 上滚動，並藉由使加熱器進行加熱使熱可塑性樹脂產生熱 變形來形成凹凸構造。或者是伴隨著模具的按壓，從透明 基板側照射紅外線，藉此將熱賦予至熱硬化性樹脂使其變 形。或者是將上述模具固定，並將層合有透明樹脂層前驅 物之透明基板送入於此等之間。 -28- 201133901 上述方法中，係一邊進行塗佈來形成樹脂層一邊使樹 脂硬化，但因情況的不同，亦可在形成一定區域後再硬化 。在連續性的形成作業或是樹脂層形成程序的高速化中， 可依據UV照射來進行硬化之紫外線硬化型樹脂較爲適合 。再者，其他樹脂中，亦可例如在溶解於溶劑之狀態下塗 佈，然後使溶劑氣化而藉此形成。 此外’凹凸的形成亦可不依據模具，亦可藉由網版印 刷、平版印刷等之印刷法來形成。此時，可在印刷中或印 刷後使樹脂層硬化。 當形成底層時’底層的形成方法並無特別限定，可從 以往的塗佈法中選擇適合者。具體而言，可使用網版印刷 等之印刷法、凹版塗佈法、逆向塗佈法、棒塗佈法、噴霧 塗佈法、刮刀塗佈法、輥塗佈法、壓模塗佈法等，因應條 件的不同，亦可使用淋幕塗佈法（流動塗佈法）、旋轉塗 佈法等。 再者，關於形成細微凹凸構造之製法的一型態，係參 照圖面更具體地說明。第1 〇圖及第11圖係顯示本發明之保 護基板的製造步驟之模式圖。首先如第ίο圖所示，藉由分 注或噴墨法’從噴嘴或噴頭4以點狀將樹脂液2滴下或噴射 至透明基板1的表面並進行塗佈。此時所塗佈之樹脂液2的 形狀，爲可使液體滴下之形狀，較佳爲半球或是裁切球的 一部分後之形狀。此時’係從紫外線光源5將紫外線6照射 至剛塗佈後之樹脂液以使其立即硬化。 此外’透明基板1藉由圖中未顯示的搬運裝置往箭頭 -29- 201133901 10的方向被搬運，然後如第η圖所示，藉由調整塗佈速度 與搬運速度，可連續地以預定間隔來塗佈樹脂液2 ’而形 成凸部2。 各個凸部（點）2的大小，係由樹脂的黏度、流變減 黏性、噴嘴徑、溫度、吐出壓力等因素來決定，可在半徑 10微米至100微米的大小之間自由地調整。 上述方法中，係一邊塗佈一邊使樹脂硬化，但因情況 的不同，亦可在形成一定區域後再硬化。此外，硬化的方 法，除了上述照射紫外線之方法之外，若爲熱硬化樹脂， 亦可進行加熱》在連續性的形成作業或是樹脂形成程序的 高速化中，可依據UV照射來進行硬.化之紫外線硬化型樹 脂較爲適合。爲熱硬化樹脂時，可將事前經加熱使黏度降 低之狀態的樹脂塗佈於基板表面，然後加熱使其硬化而形 成細微凹凸構造。再者，其他樹脂中，亦可例如在溶解於 溶劑之狀態下塗佈，然後使溶劑氣化而藉此形成。 此外，在形成細微凹凸構造前，如上述般，可預先於 基板上形成底層。底層的形成方法並無特別限定，可從以 往的塗佈法中選擇適合者。具體而言，可使用網版印刷等 之印刷法、凹版塗佈法、逆向塗佈法、棒塗佈法、噴霧塗 佈法、刮刀塗佈法、輥塗佈法、壓模塗佈法等，因應條件 的不同，亦可使用淋幕塗佈法（流動塗佈法）、旋轉塗佈 法等。 如上述般，根據本發明之方法，可連續地製造出細微 凹凸構造，極爲容易進行量產化。此外，亦具有可在低製 -30- 201133901 造成本下進行之優點。 [實施例] [實施例1] 首先將甲基丙烯酸三氟乙酯（商品名稱「Fluor j ’Tosoh F-Tec公司製）15重量份及二茂駄型光聚合 劑（商品名稱「Irgacure 784」，Ciba-Geigy公司製） 攪拌於聚二甲基丙烯酸乙二醇酯（商品名稱「NK 4G」，新中村化學公司製）8 3重量份而得紫外線硬化 脂。 接著製備使Teflon (註冊商標）含浸於玻璃布並 燒結所成之T e fl ο η (註冊商標）薄片。表面爲玻璃布 目呈壓花形狀，該間距爲200微米，深度爲5〇微米。 Teflon (註冊商標）薄片捲取於橡膠製的輥而製作出 。因此，凹凸的數目爲每1平方公分2500個。 接著製備白板玻璃，藉由滴管將所製備的紫外線 性樹脂塗佈於該一邊附近。然後從塗佈有樹脂之一邊 模具，並朝向相對向的邊滾動。同時夾持白板玻璃並 具的正下方設置高壓水銀燈，配合著模具的按壓來進 脂的硬化。 如上述般，係調查以透明樹脂形成細微凹凸紋理 板玻璃的特性。 本實施例所使用之透明樹脂硬化物的折射率爲1 此外，凸部的形狀爲四角錐狀，該斜面的角度，與白 ester 起始 混合 Ester 性樹 進行 的網 將該 模具 硬化 按壓 在模 行樹 之白 • 47。 板玻 -31 - 201133901 璃平面約呈30度。此外，該硬度以鉛筆硬度計爲5H的硬度 。上述所得之細微凹凸紋理的構成面（斜面），與基板法 線所成的角均爲60度以下，占凹凸構造全體的100%。 本實施例中，係從相對於在表面上形成有細微凹凸紋 理之白板玻璃呈45度的角度使光入射，使用分光高度計測 定其折射光量，並與表面上未形成紋理之白板玻璃比較， 當以未形成紋理之玻璃的穿透光量爲100時，可得106的穿 透光量。 此外，根據本發明，在紫外線硬化性樹脂的硬化時使 用模具，可進行不受到氧阻礙之紫外線硬化，硬化速度與 不使用模具之狀態相比，大約快2成。 再者，即使將丙烯酸單體般之揮發性高的成分用作爲 紫外線硬化性樹脂的原料，亦可藉由使用模具，可在不產 生氣化下硬化，而能夠在完全不產生樹脂的缺陷或大氣污 染等來進行加工。 再者，藉由使用模具，可大幅限制雜質的捲入，而能 夠設置高品質之紋理層》 [實施例2] 使用絲網版印刷用的版（開口尺寸30~100微米），在 不設置遮罩下，藉由一般所知的方法將實施例1之印刷在 厚度約50〜100微米之丙烯酸系透明樹脂薄膜上。 結果可得知前述樹脂如網版網目的開口圖型般地被轉 印。此外’紋理構造的高度，可藉由版厚與樹脂的黏度、 -32- 201133901 所使用之溶劑與硬化速度，調製爲數微米至數百微米，形 狀亦可調製爲近似於剖面半圓狀至圓錐狀之形狀。 [實施例3] 首先將甲基丙烯酸甲酯（Kuraray公司製）15重量份 、二茂鈦型光聚合起始劑（商品名稱「Irgacure 784」， Ciba-Geigy公司製）1重量份，與用以賦予流變減黏性之 Aerosil (商品名稱「Aerosil 90」，Evonik公司製）2重量 份混合攪拌於聚二甲基丙烯酸乙二醇酯（商品名稱「NK Ester 4 G」，新中村化學公司製）8 2重量份而得紫外線硬 化樹脂組成物。 接著製備3 00毫米見方的白板玻璃，使用分注器，以 300微米的間距將2奈升（Nanoliter)液量的樹脂塗佈於全 面上。分注針使用Musashi Enigneering公司製的高精細噴 嘴FN-0.02N。被吐出之樹脂的形狀爲半徑約ι〇〇微米之半 球狀。此外，於噴嘴的旁邊配置作爲紫外線光源的LED光 源，並於剛被吐出後的樹脂照射硬化所需時間的紫外線， 藉此可使所形成之樹脂的半球狀形狀不會產生變形之間來 硬化。此時的紫外線’爲波長3 6 5 n m ' 4 6 0 0 m W / c m2 ( 4.6J/cm2 )。此光學半球點係以間距2 5 0微米形成於玻璃板 面，而得具有細微凹凸構造之保護玻璃。 接著評估所得之構造物的特性。硬化後之透明樹脂的 折射率爲1 · 4 9。此外’樹脂點凸部的形狀大致呈半球狀， 該硬度以錯筆硬度計爲5 Η的硬度。從相對於形成有細微凹 -33- 201133901 凸形狀之白板玻璃呈45度的角度使光入射，使用設置在玻 璃的法線方向之分光高度計測定其穿透光量，當以未形成 紋理之白板玻璃爲100時，可得103的穿透光量。此外，求 取細微凹凸形狀與基板法線所成的角爲60°以下之部分的 面積之比率，可得知其約爲13.4%。此凸部的曲率半徑 A=100.微米，切斷圓的半徑B = 50微米，B = A/2。 [實施例4] 調配90質量％的甲基丙烯酸2,2,2-三氟乙酯作爲氟化丙 烯酸單體，2質量％的2,2-二甲氧基·1，2-二苯基乙烷-】_酮 (Ciba-Geigy公司製的Irgacure 651)作爲光聚合起始劑， 8質量％的二氧化砂（£乂〇11丨1£公司製的八61"〇8丨1〇乂50)作爲 流變減黏性賦予劑，而得原料組成物。 將所得之原料組成物與實施例1相同地塗佈在基板上 。此外，與實施例1相同，使用L E D作爲紫外線照射光源 並照射在被吐出之樹脂，進行聚合硬化而得聚（甲基丙稀 酸2,2,2-三氟乙酯）的凸部。評估所得之樹脂的特性，折 射率η = 1·418，玻璃轉移溫度Tg = 69°C。此外，與實施例1 相同地評估穿透光量，可得1 04.5的穿透光量之結果。此 外，求取細微凹凸形狀與基板法線所成的角爲60°以下之 部分的面積之比率，可得知其約爲1 3.4%。此凸部的曲率 半徑A=100微米，切斷圓的半徑B = 50微米，B = A/2。 [實施例5] -34- 201133901 使用丙烯酸2,2，2 -三氟乙酯來取代實施例2的甲基丙烯 酸2,2,2-三氟乙酯作爲氟化丙烯酸單體，其他與實施例2相 同而得聚丙烯酸2,2,2-三氟乙酯樹脂的細微凹凸構造。評 估所得之構造物的特性，折射率n= 1.4 1 1，玻璃轉移溫度 Tg = -1 0。此外，與實施例1相同地評估穿透光量，可得 1 04 · 8的穿透光量之結果。此外’求取細微凹凸形狀與基 板法線所成的角爲6 0 °以下之部分的面積之比率，可得知 其約爲1 3.4 %。此凸部的曲率半徑A = 1 〇 〇微米，切斷圓的半 徑 B = 50 微米，Β = Α/ 2ο [實施例6] 調配90質量％的甲基丙烯酸2,2,2 -三氟乙酯，2質量％ 的二（4 -三級丁基環己基）過氧二碳酸酯（日本油脂公司 製的Peroyl TCP)與1質量％的三級丁基過氧_2己酸乙酯（ 日本油脂公司製的Peroxy 0)作爲熱聚合起始劑，7質量％ 的二氧化矽（Evonik公司製的Aerosil 0X50)作爲流變減 黏性賦予劑，而得原料組成物。 將所得之原料組成物與實施例1相同地塗佈在基板上 。此時’當基板爲玻璃時，係在事前加熱玻璃至1 5 〇 〇C之 狀態下塗佈原料組成物。被吐出於基板上之樹脂，係藉由 基板的熱產生硬化而形成凸部。評估所得之樹脂的特性， 折射率n= 1 _ 4 1 8 ’玻璃轉移溫度Tg = 69 °C。此外，與實施例 1相同地評估穿透光量’可得104.5的穿透光量之結果。此 外，求取細微凹凸形狀與基板法線所成的角爲6 〇。以下之 -35- 201133901 部分的面積之比率，可得知其約爲1 3.4%。此凸部的曲率 半徑A=100微米，切斷圓的半徑B = 50微米，B = A/2。 [實施例7] 實施例1、2中，係使用與凹凸構造相同的樹脂來形成 底層。底層的形成係使用噴嘴塗佈法，膜厚設爲1微米。 其他與實施例1、2相同來形成細微凹凸構造並進行評估， 可得知其成爲較實施例1、2更接近於半球狀之形狀，且穿 透光量亦增加。此外，將底層用的樹脂稀釋成適當的溶液 ，並選擇旋轉塗佈法等之塗佈法，藉此可實現數百nm的膜 厚。可得知在此膜厚下，亦可充分地達成作爲底層之功能 產業上之可利用性： 本發明之光電動勢裝置用保護基板，可較佳地用作爲 具有可提升太陽能電池的聚光效率之塗層之保護基板。此 外，光電動勢裝置用保護基板的製造方法，能夠以簡單的 方法容易地形成太陽能電池保護層，亦可運用在既有的光 電動勢裝置。本發明之光電動勢裝置用保護基板，並不限 定於單晶、多晶、非晶矽半導體型等之矽系，CIGS等之化 合物系，色相增感型與有機薄膜型等之有機矽等之發電基 板的種類，亦可較佳地運用在各種型式的太陽能電池。 【圖式簡單說明】 -36- 201133901 第1圖係顯示本發明之光電動勢裝置用保護基板的一 項型態之模式圖。 第2圖係顯示本發明之光電動勢裝置用保護基板的其 他型態之模式圖。 第3圖係顯示本發明之光電動勢裝置用保護基板的第3 型態之模式圖。 第4圖係顯示本發明之光電動勢裝置用保護基板的第4 型態之模式圖。 第5圖係顯示本發明之光電動勢裝置用保護基板之具 有底層的構成例之模式圖。 第6圖係顯示本發明之光電動勢裝置用保護基板的原 理之模式圖。 第7圖係顯示本發明之光電動勢裝置用保護基板的原 理之模式圖。 第8圖係顯示半球狀的凸部與切線之關係之模式圖。 第9圖係顯示半球狀的凸部之曲率半徑A與曲率半徑B 的關係之模式圖。 第10圖係顯示本發明之光電動勢裝置用保護基板的製 造步驟之模式圖。 第11圖係顯示本發明之光電動勢裝置用保護基板的製 造步驟之模式圖。 【主要元件符號說明】 1 :透明基板 -37- 201133901 2:透明樹脂層（凹凸構造） 4 :噴嘴或噴頭 5 :紫外線光源 101、 201、 301、 401、 501 ：透明基板 102、 202、302、402、502:形成有細微凹凸構造、 細微凹凸紋理之透明樹脂層 -38-Teflon (registered trademark) AF, Cytop-like alicyclic fluororesin manufactured by Asahi Glass Co., Ltd. Further, the active energy ray-polymerizable acrylic resin preferably contains a fluorine-based one. By making the acrylic resin contain a fluorine group, the refractive index can be easily lowered. Further, by performing fluorination, water repellency can be improved, antifouling function can be improved, and deterioration of photoelectric conversion efficiency with time can be prevented. The acrylic resin is preferably an acrylic or methacrylic polymer or a copolymer. Examples of the polymer include polymethyl methacrylate, polybutyl acrylate, polybutyl acrylate, polybutyl methacrylate, poly(octadecyl methacrylate), polymethacrylic acid. Trifluoroethyl ester, polycyclohexyl methacrylate, polyphenyl methacrylate, polyglycidyl methacrylate, and polyallyl methacrylate. Further, preferred monomers for forming a polymer or a copolymer include, for example, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, and methyl group. Butyl acrylate, butyl acrylate, glycidyl methacrylate, glycidyl acrylate, methoxyethyl methacrylate, methoxyethyl acrylate, acetone methacrylate, methyl ketone methacrylate, amyl acrylate Wait. Preferred examples of the fluorinated monomer include trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl acrylate, tetrafluoropropyl methacrylate, hexafluoroisopropyl acrylate, and methacrylic acid. Hexafluoroisopropyl ester, hexafluorobutyl methacrylate, propylene, heptafluorobutyl methacrylate, pentafluoropropyl methacrylate, pentafluoropropyl acrylate, and the like. Preferred fluorinated acrylic resins include, for example, poly(acrylic acid-20-201133901 1,1,1,3,3,3-hexafluoroisopropyl ester) n=l_3 75, Tg = -23 'poly(acrylic acid) 2,2,3,3,4,4,4-heptafluorobutyl ester)1^=1.377, D = -30, poly(methacrylic acid 2,2,3,3,4,4,4-seven Fluorobutyrate) n = 1.383, Tg = 6.5, poly(2,2,3,3,3-five acrylic acid acrylate) 11=1_389, D = -26, poly(methyl acrylate 1,1 ,1,3,3,3-hexafluoroisopropyl ester)n=l_39, Tg = 56, poly(2,2,3,4,4,4-hexafluorobutyl acrylate) n = 1.394, Tg = - 22. Poly(2,2,3,4,4,4-hexafluorobutyl methacrylate), poly(2,2,3,3,3-pentafluoropropyl methacrylate) n=1.395, Tg = 70, poly(2,2,2-trifluoroethyl acrylate) n=1.411, Tg = -i〇, poly(2,2,3,3-tetrafluoropropyl acrylate)η = 1·415, § = -22, poly(2,2,3,3-tetrafluoropropyl methacrylate) 11=1.417, Dinglu = 68, poly(2,2,2-trifluoroethyl methacrylate) 11= 1.418 'Ding 8=69 and so on. In these resins, the refractive index η is 1.42 or less 'especially 1.4 Å or less', so that the effect of lowering the surface reflectance by the low refractive index can be expected. The number average molecular weight of the polymer is usually from about 5 Å to 500,000 g/mole, and the weight average molecular weight of the polymer is from about 10,000 to about 1,000,000. In order to obtain the above resin material, for example, an exemplified monomer or the like can be polymerized and cured by a generally known method to form a polymer. Specifically, a method in which a thermal polymerization initiator which generates a radical by heating is added to a monomer composition in advance, followed by heating to carry out polymerization (hereinafter referred to as "thermal polymerization"), and A method in which a photopolymerization initiator which generates a radical by an active energy ray such as ultraviolet rays is added to a monomer composition and then irradiated with an active energy ray to carry out polymerization (hereinafter referred to as "photopolymerization"), etc. And a method of performing polymerization by previously adding a radical polymerization initiator. In the present invention, photopolymerization is particularly preferred. -21 - 201133901 Further, in order to easily form the shape of the convex portion, it is also effective to add a rheological viscosity reducing agent. The rheological viscosity reducing imparting agent may be any inorganic fine particles having a large surface area. For example, the fine particle powder added for the purpose is preferably an inorganic fine particle synthesized by a gas phase reaction, and for example, Fumed silica, fumed bismuth pentoxide, fumed titanium dioxide, and the like. Specifically, aluminum silicate (Aerosil MOX170), aluminum oxide (Aerooxide Alu C) or titanium dioxide (Aero-oxide Ti02 P25) or a dioxide pin (OZC-8YC manufactured by Sumitomo Osaka Cement Co., Ltd. or Tosoh Co., Ltd.) can be used. TZ-8Y), etc., may be used alone or in combination of two or more kinds, and the amount thereof is an amount of 0.1 to 10% by mass based on the total amount of the raw material resin. The raw material composition may contain various subcomponents in addition to the above rheological viscosity reducing agent. Examples of the accessory component include other monomers which can be radically polymerized, an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, a dye, a chelating agent, a decane coupling agent, a polymerization inhibitor, and a photostabilizer. The amount added is an arbitrary amount and can be added as necessary within a range that does not adversely affect the main component constituting the resin. When the transparent resin layer is formed, for example, a composition containing an exemplary monomer, a polymer or the like can be polymerized and cured to form a polymer or a copolymer by a generally known method. Specifically, a method in which a thermal polymerization initiator which generates a radical by heating is added to a monomer composition in advance, followed by heating to carry out polymerization (hereinafter referred to as "thermal polymerization"), and A photopolymerization initiator which generates a radical by an active energy ray such as ultraviolet rays is added to a polymerizable composition in advance, and then irradiated with an active energy-22-201133901 line to carry out polymerization (hereinafter referred to as "photopolymerization" In the present invention, photopolymerization is particularly preferred, and a method in which a radical polymerization initiator is added in advance to carry out polymerization. Examples of the thermal polymerization initiators include hydrogen peroxide, benzamidine peroxide (benzonitrile peroxide), diisopropyl peroxycarbonate, and tertiary butylperoxy (2-ethylhexanoate). Ester), 2,2·-azobisisobutyronitrile, 4,4'-azobis(cyclohexanecarbonitrile), 4,4'-azobis(4-cyanovaleric acid) and 2,2, An azo compound such as azobis(2-methylpropane). Other commercially available products such as Trigonox 21 and Perkadox 16 which are also organic peroxides can also be used as starting materials. The above thermal polymerization initiator may be used singly or in combination of two or more. The amount of the thermal polymerization initiator to be added is usually 0,0 1 to 2 0% by mass based on the total amount of the monomers. Further, examples of the photopolymerization initiator include diphenyl ketone, benzoin ethyl ether, benzoin propyl ether, diethoxy acetophenone, 1-hydroxycyclohexyl benzophenone, and 2,6-dimethylbenzyl fluorenyl group. Diphenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2-hydroxy-l-{4-[4-(2-hydroxy-2-methyl-propyl Mercapto)-benzylmethyl]phenyl}-2-methyl-propane-butanone, benzyldimethylketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2 -propyl)ketone, 2-methyl-2-morpholinyl (4-thiomethylphenyl)propane-1. ketone, and the like. In particular, it is not particularly limited as long as it is a radical photopolymerization initiator, preferably hydroxy-bu {4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl }_2-Methyl-propane-1-one (trade name: Irgacure 127) and the like. In addition, the storage stability after the preparation is good. -23- 201133901 The above photopolymerization initiators may be used alone or in combination of two or more. The amount of the photopolymerization initiator to be added is usually 0.01 to 10% by mass based on the total amount of the monomers. When the amount of the photopolymerization initiator added is too large, the polymerization proceeds violently, which may cause adverse effects in terms of optical characteristics, strength, and the like. On the other hand, if it is too small, there is a fear that the raw material composition may not be sufficiently polymerized. The amount of the active energy ray to be irradiated may be any amount as long as the photopolymerization initiator can generate a radical, but in a very small amount, the polymerization is incomplete, and the heat resistance of the cured product cannot be sufficiently exhibited. The mechanical properties, on the other hand, when extreme excess is caused, deterioration due to light such as yellowing of the cured product occurs, so that the composition of the monomer and the kind and amount of the photopolymerization initiator can be blended, preferably, for example, 0.1 to 0.10. Ultraviolet rays of 200 to 400 nm are irradiated in a range of 200 J/cm 2 . It is especially preferred to divide the active energy lines into a plurality of times. That is, 'the first irradiation is 1 / 20 to 1 / 3 of the total irradiation amount, and the remaining amount is required to be irradiated after the second time, so that a cured product having a smaller complex refractive index can be obtained. The irradiation time can be appropriately adjusted in accordance with the amount of resin and the degree of hardening. It is usually adjusted between 1 second and 1 minute. For the light source to be used, LEDs (light-emitting diodes) such as ultraviolet LEDs, blue LEDs, and white LEDs, xenon lamps, carbon arcs, germicidal lamps, ultraviolet fluorescent lamps, constant-pressure mercury lamps, and high-pressure mercury lamps for photocopying can be used. Medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high pressure mercury lamp, electrodeless lamp, xenon lamp, wedding lamp 'metal_chemical lamp, gas lamp, excimer lamp made by Toshiba Harrison Lighting Co., Ltd., xenon lamp made by Fusi ο η company, Η P 1 us lamp, D lamp, V lamp, Q lamp, M lamp, etc.' or sunlight, or an electronic wire formed by sweeping -24-201133901, screen-type electron line acceleration path, etc. . Further, in order to sufficiently harden, an active energy ray such as an ultraviolet ray may be irradiated in an inactive environment such as nitrogen. Photopolymerization and thermal polymerization can be carried out simultaneously for the purpose of rapidly completing the polymerization. At this time, the polymerizable composition can be heated to be cured in the range of 30 to 300 ° C while being irradiated with the active energy ray. At this time, a thermal polymerization initiator for completing the polymerization may be added to the raw material composition, but when it is added in a large amount, there is a concern that adverse effects are caused as described above, so the thermal polymerization initiator at this time is relative to the raw material. The total amount of the resin can be used in the range of 0.1 to 2% by mass. The raw material composition can be dissolved in a solvent for use. The solvent is not particularly limited, and the optimum one can be selected as necessary. Specifically, an alcohol such as an alcohol or an unsaturated alcohol or an organic solvent can be used. In the present invention, a primer layer may be formed between the substrate and the fine uneven layer. By forming the underlayer, the wettability of the substrate can be improved, the contact angle with the coating liquid can be increased, and the coating liquid can be formed closer to the hemisphere. Further, it is expected to improve the adhesion to the fine uneven layer and to improve the refractive index on the portion having no uneven structure. At this time, as shown in Fig. 5, the protective substrate for the photovoltaic device has a transparent substrate 510 and a bottom layer 503 formed on the transparent substrate, and then a fine uneven structure 502 is formed thereon. The bottom layer is not particularly limited, and is preferably a material having a high contact angle. Specifically, the contact angle with respect to water must be a contact angle (30°) or more of a general glass, preferably 60° or more. It is 70° or more, and particularly preferably 80° or more. As such a material, for example, a resin material of the above-mentioned fine concavo-convex structure, -25-201133901, particularly a fluorine-based resin, particularly a fluorine-based acrylic resin, may be mentioned. This material is also preferable from the viewpoint of adhesion to a fine concavo-convex structure, and it is particularly preferable to use a material which is the same or the same as the fine concavo-convex structure. The film thickness of the underlayer is not particularly limited, and the thinner the film, the better the film thickness can be adjusted depending on the characteristics of the formation method or the material to be used, the required optical characteristics, durability, and the like. In general, for the purpose of improving the wettability and improving the adhesion, it may be from about 1 nm to several 1 μm, and the upper limit is preferably about several millimeters. When the protective substrate for a photovoltaic device of the present invention is produced, a transparent resin having the same or lower refractive index as that of the transparent substrate can be laminated on the transparent substrate disposed on the photosensitive portion, and the surface of the transparent resin layer can be formed into a fine shape. The unevenness 'cures the transparent resin layer at any stage after formation or after formation', and a fine uneven structure is formed on the surface of the transparent resin layer. Specifically, the transparent resin before curing is formed on the surface of the transparent substrate by a coating method, a coating method, a printing method, a dipping method, or the like to form a transparent resin layer precursor, and then a mold or the like is used. The member which forms the unevenness is formed by pressing on the precursor, and then polymerizing and hardening by a predetermined method to form a transparent resin layer. When a transparent resin is formed by an ultraviolet curable resin, a transparent resin layer precursor is formed by first laminating a transparent resin material having an ultraviolet curable resin onto a surface of a transparent substrate by coating or the like. Then, the mold having the fine uneven texture is pressed against the transparent resin layer precursor to be formed, and at the same time or thereafter, ultraviolet rays are irradiated to cure the transparent resin. The mold for forming the fine concavo-convex structure is not particularly limited, and it is possible to use a mold used in a printing method or the like, or various pressing molds, in -26-201133901. The shape may be a flat shape or a roll type, and may be configured to be suitable for manufacture. For example, a sheet formed by sintering and sintering Teflon (registered trademark) can be used for winding into a roll type mold such as rubber. When a roll type mold is used, it can be formed by printing. Specifically, the mold is rolled on a transparent substrate on which a transparent tree is formed, and the transparent resin is cured from the inner surface of the transparent substrate. Alternatively, the mold is fixed to ultraviolet rays, and a transparent substrate or the like of a transparent resin layer precursor is laminated. Further, a rigid body having a plurality of lateral grooves or irregularities may be rotated to form irregularities, or a linear shape, a metal wire, or a resin wire may be arranged in the vertical and horizontal directions and pressed. Further, the surface may be scraped or cut by a plurality of hooks or protrusions of the rigid body. Further, after the transparent resin is laminated, the concave and convex portions may be formed by a photomask method. That is, when a film of a curable transparent resin is formed by a photomask method, it is covered with a mask of a pattern to be formed, and then the transparent resin of the convex portion is hardened by irradiation of light or radiation. . Further, it is hardened by scanning a visible light laser or the like while using a scanning mirror or an XY dot plotter in accordance with photo molding. That is, according to the concave energy line scanning, the surface of the resin formed is irradiated, and the shape of the convex shape of the hard mold is immersed in the roll of the glass, and the technical layer of the pre-exposure ultraviolet ray generating means of the brushing method is sent thereto. The filament-like fine is formed by formation. The method or the luminescence, when the energy of the concave and convex shape is linear, the ultraviolet ray or the convex shape will be formed to form the ridge -27-201133901. Further, it may be formed by irradiating a heat-generating energy ray such as an infrared laser or the like with the following thermosetting resin or thermoplastic resin. When the transparent resin layer is formed by a thermosetting resin, fine irregularities are formed on the transparent resin layer precursor in the same manner as described above, and then heated at the same time or thereafter to cure the transparent resin. When a thermosetting resin is used, the mold wound around the metal roller with the heater can be rolled on the transparent substrate on which the transparent resin layer precursor is formed, and the heat is imparted to the heater by heating the heater to The thermosetting resin is thermally cured. Alternatively, the infrared rays are irradiated from the transparent substrate side along with the rolling of the mold, whereby heat is applied to the thermosetting resin to be cured. Alternatively, the mold or the mold may be fixed to an infrared ray generating means, and a transparent substrate on which a transparent resin layer precursor is laminated may be fed between. When the transparent resin layer is formed by a thermoplastic resin, the resin which has been heated to reduce the viscosity in advance can be applied to the surface of the transparent substrate to form a transparent resin layer precursor. Alternatively, after dissolving the transparent resin in a solvent, it is applied onto a transparent substrate, and then the solvent is vaporized to form a transparent resin layer. When a thermoplastic resin is used, as in the above-described thermosetting resin, a roll type mold can be rolled on a transparent substrate on which a transparent resin layer precursor is formed, and the thermoplastic resin is heated by heating the heater. Deformed to form a relief structure. Alternatively, the infrared rays are irradiated from the transparent substrate side with the pressing of the mold, whereby heat is applied to the thermosetting resin to be deformed. Alternatively, the mold is fixed, and a transparent substrate on which a transparent resin layer precursor is laminated is fed between. -28-201133901 In the above method, the resin is cured while being applied to form a resin layer. However, depending on the case, it may be hardened after forming a certain region. In the continuous forming operation or the speeding up of the resin layer forming process, an ultraviolet curable resin which can be cured by UV irradiation is suitable. Further, other resins may be formed by, for example, coating in a state of being dissolved in a solvent, and then vaporizing the solvent. Further, the formation of the concavities and convexities may be formed by a printing method such as screen printing or lithography, without depending on the mold. At this time, the resin layer can be hardened during printing or after printing. When the underlayer is formed, the method of forming the underlayer is not particularly limited, and a suitable one can be selected from the conventional coating methods. Specifically, a printing method such as screen printing, a gravure coating method, a reverse coating method, a bar coating method, a spray coating method, a knife coating method, a roll coating method, a die coating method, or the like can be used. Depending on the conditions, a curtain coating method (flow coating method), a spin coating method, or the like can also be used. Further, a type of the method for forming a fine concavo-convex structure is more specifically described with reference to the drawings. Fig. 1 and Fig. 11 are schematic views showing the steps of manufacturing the protective substrate of the present invention. First, as shown in Fig. ί, the resin liquid 2 is dropped or sprayed from the nozzle or the head 4 in a dot shape onto the surface of the transparent substrate 1 by coating or spraying. The shape of the resin liquid 2 applied at this time is a shape which allows the liquid to drip, and is preferably a hemisphere or a shape in which a part of the ball is cut. At this time, the ultraviolet ray 6 is irradiated from the ultraviolet light source 5 to the resin liquid immediately after application to be immediately hardened. Further, the 'transparent substrate 1 is transported in the direction of the arrow -29-201133901 10 by a transport device not shown in the figure, and then, as shown in the figure n, can be continuously spaced at predetermined intervals by adjusting the coating speed and the transport speed. The resin liquid 2' is applied to form the convex portion 2. The size of each convex portion (dot) 2 is determined by factors such as viscosity of the resin, rheological viscosity reduction, nozzle diameter, temperature, discharge pressure, and the like, and can be freely adjusted between the sizes of 10 μm to 100 μm. In the above method, the resin is cured while being applied, but depending on the case, it may be cured after forming a certain region. Further, in the method of curing, in addition to the above method of irradiating ultraviolet rays, if it is a thermosetting resin, heating may be performed. In the continuous forming operation or the speeding up of the resin forming process, it may be hardened by UV irradiation. The ultraviolet curable resin is suitable. In the case of a thermosetting resin, a resin which has been heated to reduce the viscosity in advance may be applied to the surface of the substrate, and then heated and cured to form a fine concavo-convex structure. Further, other resins may be formed by, for example, coating in a state of being dissolved in a solvent, and then vaporizing the solvent. Further, before forming the fine concavo-convex structure, as described above, the underlayer may be formed in advance on the substrate. The method for forming the underlayer is not particularly limited, and a suitable one can be selected from the conventional coating methods. Specifically, a printing method such as screen printing, a gravure coating method, a reverse coating method, a bar coating method, a spray coating method, a knife coating method, a roll coating method, a die coating method, or the like can be used. Depending on the conditions, a curtain coating method (flow coating method), a spin coating method, or the like can also be used. As described above, according to the method of the present invention, the fine concavo-convex structure can be continuously produced, and mass production is extremely easy. In addition, it also has the advantage of being able to perform in the low system -30-201133901. [Examples] [Example 1] First, 15 parts by weight of trifluoroethyl methacrylate (trade name "Fluor j 'Tosoh F-Tec") and a hafnocene type photopolymerization agent (trade name "Irgacure 784" (Ciba-Geigy Co., Ltd.) 80 parts by weight of polyethylene glycol dimethacrylate (trade name "NK 4G", manufactured by Shin-Nakamura Chemical Co., Ltd.) was stirred to obtain ultraviolet curable fat. Next, a T e fl ο η (registered trademark) sheet obtained by impregnating Teflon (registered trademark) with a glass cloth and sintering was prepared. The surface is embossed in glass cloth with a pitch of 200 microns and a depth of 5 microns. Teflon (registered trademark) sheets were taken up from rubber rolls to make them. Therefore, the number of the concavities and convexities is 2,500 per 1 cm 2 . Next, white plate glass was prepared, and the prepared ultraviolet resin was applied to the vicinity of the side by a dropper. The mold is then coated from one of the sides of the resin and rolled toward the opposite sides. At the same time, the high-pressure mercury lamp is placed directly under the whiteboard glass, and the hardening of the fat is carried out in conjunction with the pressing of the mold. As described above, the characteristics of forming a fine uneven textured sheet glass with a transparent resin were investigated. The cured resin of the transparent resin used in the present embodiment has a refractive index of 1 . Further, the shape of the convex portion is a quadrangular pyramid shape, and the angle of the inclined surface is combined with the white ester to start the Ester tree to harden the mold and press the mold. White of the tree • 47. Plate glass -31 - 201133901 The glass plane is about 30 degrees. Further, the hardness was a hardness of 5H in terms of pencil hardness. The constituent surface (bevel) of the fine uneven texture obtained as described above has an angle of 60 degrees or less with respect to the substrate normal, and accounts for 100% of the entire uneven structure. In this embodiment, the light is incident at an angle of 45 degrees with respect to the whiteboard glass on which the fine uneven texture is formed on the surface, and the amount of the refracted light is measured using a spectrophotometer, and compared with the whiteboard glass on the surface which is not textured. When the amount of transmitted light of the untextured glass is 100, the amount of transmitted light of 106 is obtained. Further, according to the present invention, the mold can be used in the curing of the ultraviolet curable resin, and the ultraviolet curing can be performed without being inhibited by oxygen, and the curing speed is about 20% faster than the state in which the mold is not used. Further, even if a component having a high volatility such as an acrylic monomer is used as a raw material of the ultraviolet curable resin, it is possible to use a mold to harden without generating gasification, and it is possible to prevent defects of the resin at all or Air pollution, etc. are processed. Further, by using a mold, it is possible to greatly restrict the entrapment of impurities, and it is possible to provide a high-quality texture layer. [Example 2] A plate for screen printing (opening size: 30 to 100 μm) is not provided. Under the mask, the film of Example 1 was printed on an acrylic transparent resin film having a thickness of about 50 to 100 μm by a generally known method. As a result, it was found that the aforementioned resin was transferred as in the opening pattern of the screen. In addition, the height of the texture structure can be adjusted to a few micrometers to hundreds of micrometers by the thickness of the plate and the viscosity of the resin, and the solvent and hardening speed used in -32-201133901. The shape can also be modulated to approximate the semicircular shape to the cone. Shape shape. [Example 3] First, 15 parts by weight of a methyl methacrylate (manufactured by Kuraray Co., Ltd.) and a titanocene type photopolymerization initiator (trade name "Irgacure 784", manufactured by Ciba-Geigy Co., Ltd.) were used in an amount of 1 part by weight. 2 parts by weight of Aerosil (trade name "Aerosil 90", manufactured by Evonik Co., Ltd.), which imparts rheological viscosity reduction, was mixed and stirred in polyethylene glycol dimethacrylate (trade name "NK Ester 4 G", Shin-Nakamura Chemical Co., Ltd. 8 parts by weight of an ultraviolet curable resin composition. Next, a 300 mm square whiteboard glass was prepared, and a nanoliter liquid resin was applied to the entire surface at a pitch of 300 μm using a dispenser. The dispensing needle used a high-fine nozzle FN-0.02N manufactured by Musashi Enigneering Co., Ltd. The shape of the resin to be discharged is a hemisphere having a radius of about ι 〇〇. Further, an LED light source as an ultraviolet light source is disposed beside the nozzle, and the ultraviolet ray is irradiated with the resin immediately after being ejected, whereby the hemispherical shape of the formed resin can be hardened without being deformed. . The ultraviolet ray at this time is a wavelength of 3 6 5 n m ' 4 6 0 0 m W / c m2 (4.6 J/cm 2 ). This optical hemispherical point was formed on the surface of the glass plate at a pitch of 250 μm to obtain a protective glass having a fine uneven structure. The properties of the resulting structure were then evaluated. The cured transparent resin has a refractive index of 1 · 49. Further, the shape of the resin dot convex portion is substantially hemispherical, and the hardness is 5 Η hardness in terms of stagger hardness. The light is incident at an angle of 45 degrees with respect to the white glass on which the convex shape is formed by the fine concave-33-201133901, and the amount of light transmitted is measured by using a spectrophotometer set in the normal direction of the glass, when the whiteboard glass is not textured. When it is 100, the amount of transmitted light of 103 can be obtained. Further, the ratio of the area of the portion where the fine uneven shape and the normal line of the substrate were 60 or less was obtained, and it was found to be about 13.4%. The convex portion has a radius of curvature A = 100 μm, and the radius of the cut circle B = 50 μm, B = A/2. [Example 4] A 90% by mass of 2,2,2-trifluoroethyl methacrylate was formulated as a fluorinated acrylic monomer, and 2% by mass of 2,2-dimethoxy·1,2-diphenyl was prepared. Ethyl-]-ketone (Irgacure 651, manufactured by Ciba-Geigy Co., Ltd.) as a photopolymerization initiator, 8 mass% of silica sand (8, & 〇8丨1〇乂, manufactured by the company) 50) As a rheological viscosity reducing imparting agent, a raw material composition is obtained. The obtained raw material composition was applied onto a substrate in the same manner as in Example 1. Further, in the same manner as in Example 1, L E D was used as a light source for ultraviolet irradiation, and the resin which was discharged was irradiated and polymerized and cured to obtain a convex portion of poly(methyl 2,2,2-trifluoroethyl methacrylate). The properties of the obtained resin were evaluated, the refractive index η = 1.418, and the glass transition temperature Tg = 69 °C. Further, the amount of transmitted light was evaluated in the same manner as in Example 1, and the result of the amount of transmitted light of 104.5 was obtained. Further, the ratio of the area of the portion where the fine concavo-convex shape and the normal line of the substrate were 60 or less was obtained, and it was found to be about 13.4%. The radius of curvature of this convex portion is A = 100 μm, and the radius of the cut circle is B = 50 μm, B = A/2. [Example 5] -34-201133901 2,2,2-trifluoroethyl acrylate was used instead of 2,2,2-trifluoroethyl methacrylate of Example 2 as a fluorinated acrylic monomer, and other implementations In the same manner as in Example 2, the fine uneven structure of the polyacrylic acid 2,2,2-trifluoroethyl ester resin was obtained. The properties of the resulting structure were evaluated, refractive index n = 1.4 1 1, glass transition temperature Tg = -1 0. Further, the amount of transmitted light was evaluated in the same manner as in Example 1, and the result of the amount of transmitted light of 1 04·8 was obtained. Further, the ratio of the area of the portion where the fine concavo-convex shape and the substrate normal are 60 ° or less is obtained, and it is found to be about 13.4%. The convex portion has a radius of curvature A = 1 〇〇 micrometer, the radius of the cut circle B = 50 μm, Β = Α / 2ο [Example 6] Formulation of 90% by mass of 2,2,2-trifluoroethyl methacrylate Ester, 2% by mass of bis(4-tributylcyclohexyl)peroxydicarbonate (Peroyl TCP manufactured by Nippon Oil & Fats Co., Ltd.) and 1% by mass of ethyl ternary butylperoxy-2-hexanoate (Japan) Peroxy 0) manufactured by Oils and Fats Co., Ltd. As a thermal polymerization initiator, 7 mass% of cerium oxide (Aerosil 0X50 manufactured by Evonik Co., Ltd.) was used as a rheological viscosity reducing agent to obtain a raw material composition. The obtained raw material composition was applied onto a substrate in the same manner as in Example 1. At this time, when the substrate is glass, the raw material composition is applied while heating the glass to 15 〇 〇C in advance. The resin which is discharged from the substrate is hardened by heat of the substrate to form a convex portion. The properties of the obtained resin were evaluated, and the refractive index n = 1 _ 4 1 8 ' glass transition temperature Tg = 69 °C. Further, the same as in Example 1, the amount of transmitted light was evaluated as a result of the amount of transmitted light of 104.5. Further, the angle formed by the fine concavo-convex shape and the substrate normal is 6 〇. The ratio of the area of -35- 201133901 below is known to be approximately 13.4%. The radius of curvature of this convex portion is A = 100 μm, and the radius of the cut circle is B = 50 μm, B = A/2. [Example 7] In Examples 1 and 2, the same layer of resin as the uneven structure was used to form the underlayer. The formation of the underlayer was carried out by a nozzle coating method, and the film thickness was set to 1 μm. In the same manner as in the first and second embodiments, the fine concavo-convex structure was formed and evaluated, and it was found that it was closer to the hemispherical shape than the first and second embodiments, and the amount of transmitted light was also increased. Further, the resin for the underlayer is diluted into an appropriate solution, and a coating method such as a spin coating method is selected, whereby a film thickness of several hundred nm can be achieved. It is understood that the usability of the functional industry as the underlayer can be sufficiently achieved under the film thickness: The protective substrate for the photovoltaic device of the present invention can be preferably used as a concentrating efficiency for improving the solar cell. The protective substrate of the coating. Further, in the method for manufacturing a protective substrate for a photovoltaic device, the solar cell protective layer can be easily formed by a simple method, and can be applied to an existing photovoltaic device. The protective substrate for a photovoltaic device of the present invention is not limited to a single crystal, a polycrystalline or an amorphous germanium semiconductor type, a compound such as CIGS, a hue sensitizing type or an organic thin film type or the like. The type of power generation substrate can also be preferably used in various types of solar cells. [Brief Description of the Drawings] -36-201133901 Fig. 1 is a schematic view showing a state of a protective substrate for a photovoltaic device according to the present invention. Fig. 2 is a schematic view showing another mode of the protective substrate for the photovoltaic device of the present invention. Fig. 3 is a schematic view showing a third type of a protective substrate for a photovoltaic device according to the present invention. Fig. 4 is a schematic view showing a fourth type of the protective substrate for the photovoltaic device according to the present invention. Fig. 5 is a schematic view showing a configuration example of a protective substrate for a photovoltaic device according to the present invention having a bottom layer. Fig. 6 is a schematic view showing the principle of a protective substrate for a photovoltaic device according to the present invention. Fig. 7 is a schematic view showing the principle of a protective substrate for a photovoltaic device according to the present invention. Fig. 8 is a schematic view showing the relationship between the hemispherical convex portion and the tangent. Fig. 9 is a schematic view showing the relationship between the radius of curvature A of the hemispherical convex portion and the radius of curvature B. Fig. 10 is a schematic view showing a manufacturing step of a protective substrate for a photovoltaic device according to the present invention. Fig. 11 is a schematic view showing a manufacturing step of a protective substrate for a photovoltaic device according to the present invention. [Description of main component symbols] 1 : Transparent substrate - 37 - 201133901 2: Transparent resin layer (concave structure) 4 : Nozzle or nozzle 5 : Ultraviolet light sources 101, 201, 301, 401, 501: Transparent substrates 102, 202, 302, 402, 502: a transparent resin layer formed with a fine uneven structure and a fine uneven texture-38-

Claims (1)

201133901 七、申請專利範圍： 1· 一種光電動勢裝置用保護基板，其係爲具有透明樹 目旨層’該透明樹脂層於配置在感光部之透明基板的表面上 具有凹凸構造，且 該透明樹脂層的折射率係與前述透明基板的折射率相 同或以下。 2 ·如申請專利範圍第1項之光電動勢裝置用保護基板 ’其中前述透明基板係由玻璃所形成。 3 ·如申請專利範圍第1項之光電動勢裝置用保護基板 ’其中前述透明樹脂層係藉由樹脂或樹脂及無機物所形成 〇 4 .如申請專利範圍第1項之光電動勢裝置用保護基板 ’其中構成前述凹凸構造之凸部面的切線與相對於基板面 之法線所成的角爲6 0度以下之部分的面積爲全部凹凸構造 面積的5 %以上。 5. 如申請專利範圍第1項之光電動勢裝置用保護基板 ’其中則述凹凸構造在前述透明基板的法線方向上之剖面 形狀爲近似於圓的一部分之形狀或近似於三角形之形狀， 此等之底面的大小’以直徑表示時爲2〇〇ηιη〜10〇〇μΐΏ 凸部的數目係每1平方公分爲1〜2.5 χ1〇9個。 6. 如申請專利範圍第1項之光電動勢裝置用保護基板 ，其中前述凹凸的平均大小爲2mm以下。 7·如申請專利範圍第丨項之光電動勢裝置用保護基板 -39- 201133901 ，其中前述透明樹脂層係具有熱或光硬化樹脂。 8. —種光電動勢裝置用保護基板的製造方法，其係將 折射率與透明基板相同或以下之透明樹脂層合於配置在感 光部之透明基板上， 將細微的凹凸形成於前述透明樹脂層的表面， 在形成中或形成後的任一階段中使透明樹脂層硬化， 將細微的凹凸構造形成於此透明樹脂層的表面。 9. 如申請專利範圍第8項之光電動勢裝置用保護基板 的製造方法，其係將形成有細微凹凸之模具或線狀的構件 予以組合來按壓前述透明樹脂層的表面，或以具有突起或 鈎之剛性體來連續地按壓或切削，藉此形成凹部而成形爲 凹凸。 10. 如申請專利範圍第8項之光電動勢裝置用保護基板 的製造方法，其中在層合前述透明樹脂後，藉由光罩法或 光成形法成形爲凹凸。 11. 如申請專利範圍第8項之光電動勢裝置用保護基板 的製造方法，其係藉由印刷法將前述透明樹脂層合於細微 的凹凸圖型而形成爲凹凸。 12. 如申請專利範圍第8項之光電動勢裝置用保護基板 的製造方法，其係將前述樹脂材料塗佈於透明基板上並形 成細微的凹凸構造。 13·如申請專利範圍第12項之光電動勢裝置用保護基 板的製造方法，其中前述塗佈係藉由分注器或噴墨來進行 -40- 201133901 1 4 _如申請專利範圍第8項之光電動勢裝置用保護基板 的製造方法’其中透明樹脂層係具有熱或光硬化樹脂。 1 5 ·如申請專利範圍第8至1 4項中任一項之光電動勢裝 置用保護基板的製造方法，其中構成前述細微凹凸構造之 凸部的形狀係近似於裁切球的一部分後之形狀， 此凸部的曲率半徑A與裁切後之切斷面的近似圓的半 徑B之關係，係由下列式（1 )所表示， B ^ A/2201133901 VII. Patent application scope: 1. A protective substrate for a photovoltaic device, which has a transparent tree layer. The transparent resin layer has a concave-convex structure on a surface of a transparent substrate disposed on the photosensitive portion, and the transparent resin The refractive index of the layer is the same as or lower than the refractive index of the transparent substrate. 2. The protective substrate for a photovoltaic device according to the first aspect of the invention, wherein the transparent substrate is formed of glass. 3. The protective substrate for a photoelectromotive force device according to the first aspect of the patent application, wherein the transparent resin layer is formed of a resin or a resin and an inorganic material. 4. The protective substrate for a photovoltaic device as claimed in claim 1 The area of the portion where the tangent of the convex portion surface constituting the uneven structure and the normal line with respect to the substrate surface is 60 degrees or less is 5% or more of the entire uneven structure area. 5. In the protective substrate for a photovoltaic device according to the first aspect of the invention, the cross-sectional shape of the uneven structure in the normal direction of the transparent substrate is approximately a part of a circle or a shape similar to a triangle. The size of the bottom surface is 2 〇〇 ηηη 10 〇〇 μ 以 when the diameter is expressed. The number of convex portions is 1 to 2.5 χ 1 〇 9 per 1 square centimeter. 6. The protective substrate for a photovoltaic device according to claim 1, wherein the average size of the unevenness is 2 mm or less. 7. The protective substrate for a photovoltaic device according to the ninth aspect of the invention, wherein the transparent resin layer has a heat or photohardenable resin. 8. A method of producing a protective substrate for a photovoltaic device, wherein a transparent resin having a refractive index equal to or lower than a transparent substrate is laminated on a transparent substrate disposed on the photosensitive portion, and fine irregularities are formed on the transparent resin layer. The surface of the transparent resin layer is hardened at any stage during or after formation, and a fine uneven structure is formed on the surface of the transparent resin layer. 9. The method for producing a protective substrate for a photovoltaic device according to the eighth aspect of the invention, wherein a mold having a fine unevenness or a linear member is combined to press the surface of the transparent resin layer, or has a protrusion or The rigid body of the hook is continuously pressed or cut, thereby forming a concave portion to be formed into irregularities. 10. The method for producing a protective substrate for a photovoltaic device according to claim 8, wherein the transparent resin is laminated, and then formed into irregularities by a photomask method or a photoforming method. 11. The method for producing a protective substrate for a photovoltaic device according to the eighth aspect of the invention, wherein the transparent resin is laminated to a fine uneven pattern by a printing method to form irregularities. 12. The method of producing a protective substrate for a photovoltaic device according to claim 8, wherein the resin material is applied onto a transparent substrate to form a fine uneven structure. 13. The method of manufacturing a protective substrate for a photovoltaic device according to claim 12, wherein the coating is performed by a dispenser or an inkjet -40-201133901 1 4 - as claimed in claim 8 A method of manufacturing a protective substrate for a photoelectromotive force device, wherein the transparent resin layer has a heat or photohardenable resin. The method of manufacturing a protective substrate for a photovoltaic device according to any one of claims 8 to 4, wherein the shape of the convex portion constituting the fine uneven structure is approximate to a shape of a part of the cut ball. The relationship between the radius of curvature A of the convex portion and the radius B of the approximate circle of the cut surface after cutting is expressed by the following formula (1), B ^ A/2
TW099122987A 2009-07-15 2010-07-13 Guard substrate for optical electromotive force equipment, and its production process TW201133901A (en)

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