JP5850392B2 - Glass plate - Google Patents

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JP5850392B2
JP5850392B2 JP2011204332A JP2011204332A JP5850392B2 JP 5850392 B2 JP5850392 B2 JP 5850392B2 JP 2011204332 A JP2011204332 A JP 2011204332A JP 2011204332 A JP2011204332 A JP 2011204332A JP 5850392 B2 JP5850392 B2 JP 5850392B2
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glass plate
protective film
content
component
solar cell
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JP2013063880A (en
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寛典 高瀬
寛典 高瀬
真人 六車
真人 六車
隆 村田
隆 村田
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Nippon Electric Glass Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells

Description

本発明はガラス板に関し、特に太陽電池用ガラス板、具体的にはＣＩＳ系太陽電池、ＣｄＴｅ系太陽電池等の薄膜化合物太陽電池、色素増感型太陽電池に好適なガラス板に関する。   The present invention relates to a glass plate, and more particularly to a glass plate suitable for a solar cell glass plate, specifically, a thin film compound solar cell such as a CIS solar cell or CdTe solar cell, or a dye-sensitized solar cell.

家庭の屋根等に設置される太陽電池等には、風雪等に対する強度、雹や砂塵等に対する耐傷性が求められる。このため、太陽電池は、発電素子を２枚のガラス板で挟み込んだ構造を有している。   A solar cell or the like installed on a home roof or the like is required to have strength against wind and snow and scratch resistance against hail and dust. For this reason, the solar cell has a structure in which the power generation element is sandwiched between two glass plates.

更に、太陽電池に用いるガラス板を製造する際は、ガラス板に傷が付かないように細心の注意を払う必要がある。一旦、ガラス板に傷が付いてしまうと、その傷を起点としてクラックが進展し、ガラス板が割れ易い状態になるからである。   Furthermore, when manufacturing the glass plate used for a solar cell, it is necessary to pay close attention not to damage the glass plate. This is because once the glass plate is scratched, cracks start from the scratch and the glass plate is easily broken.

特開平２−１２０２５６号公報JP-A-2-120256 特開平２−１４８４１号公報JP-A-2-14841 国際公開第２００８／１２０５３５号パンフレットInternational Publication No. 2008/120535 Pamphlet

特許文献１〜３には、成形工程直後にガラス板の表面に保護膜を付けると、ガラス板を製造する際に、ガラス板に傷が付き難くなることが開示されている。しかし、これらの保護膜は、ガラス板の洗浄工程で容易に消失してしまい、ガラス板の運搬時、太陽電池の製造時、太陽電池の運搬時、太陽電池の施工時、或いは太陽電池の施工後に、ガラス板に傷が付く事態を防止することができない。   Patent Documents 1 to 3 disclose that when a protective film is attached to the surface of the glass plate immediately after the forming step, the glass plate is hardly damaged when the glass plate is manufactured. However, these protective films are easily lost in the glass plate cleaning process, and when the glass plate is transported, when the solar cell is manufactured, when the solar cell is transported, when the solar cell is applied, or when the solar cell is applied. Later, it is impossible to prevent the glass plate from being damaged.

そこで、本発明の技術的課題は、洗浄工程で保護膜が消失し難く、長期に亘って、傷が付き難いガラス板を創案することである。   Therefore, the technical problem of the present invention is to create a glass plate that is difficult to lose the protective film in the cleaning process and is not easily damaged over a long period of time.

本発明者は、鋭意検討した結果、ガラス板のガラス組成を所定範囲に規制すると共に、ガラス板の表面に保護膜を形成することにより、上記技術的課題を解決できることを見出し、本発明として提案するものである。すなわち、本発明のガラス板は、少なくとも一方の表面に保護膜を有するガラス板において、ガラス組成として、質量％で、ＳｉＯ２ ４０〜７０％、Ａｌ２Ｏ３ ６〜２０％、Ｂ２Ｏ３ ０〜１．５％、Ｎａ２Ｏ＋Ｋ２Ｏ ５〜３０％、Ｎａ２Ｏ ５〜２０％、ＳｒＯ＋ＢａＯ １０〜４０％を含有し、保護膜がＳｒ含有硫酸塩及び／又はＢａ含有硫酸塩を含み、且つ薄膜化合物太陽電池に用いることを特徴とする。ここで、「Ｎａ２Ｏ＋Ｋ２Ｏ」は、Ｎａ２ＯとＫ２Ｏの合量を指す。「ＳｒＯ＋ＢａＯ」は、ＳｒＯとＢａＯの合量を指す。 As a result of intensive studies, the inventor found that the above technical problem can be solved by regulating the glass composition of the glass plate to a predetermined range and forming a protective film on the surface of the glass plate, and proposed as the present invention. To do. That is, the glass plate of the present invention is a glass plate having a protective film on at least one surface, and has a glass composition of 40% by mass, SiO 2 40-70%, Al 2 O 3 6-20%, B 2 O 3 as a glass composition. 0~1.5%, Na 2 O + K 2 O 5 ~30%, Na 2 O 5 ~20%, containing SrO + BaO 10 ~40%, a Sr-containing sulfate coercive Mamorumaku is and / or Ba-containing sulfate see containing and is characterized by using the thin-film compound solar cell. Here, “Na 2 O + K 2 O” refers to the total amount of Na 2 O and K 2 O. “SrO + BaO” refers to the total amount of SrO and BaO.

本発明のガラス板は、ガラス組成として、ＳｒＯ＋ＢａＯを１０〜４０質量％含む。このようにすれば、亜硫酸ガスをガラス板の表面に吹き付けること等により、Ｓｒ含有硫酸塩及び／又はＢａ含有硫酸塩を含む保護膜を容易に形成することができる。更に、このようにすれば、ガラス板の歪点を高めることができる。ガラス板の歪点が高いと、薄膜化合物太陽電池の製造工程において、光電変換膜の成膜温度を高温化することができ、結果として、薄膜化合物太陽電池の光電変換効率を高めることができる。 The glass plate of the present invention has a glass composition, including SrO + BaO 10 ~ 40 wt%. If it does in this way, the protective film containing Sr containing sulfate and / or Ba containing sulfate can be easily formed by spraying sulfurous acid gas on the surface of a glass plate. Furthermore, if it does in this way, the strain point of a glass plate can be raised. When the strain point of the glass plate is high, the film forming temperature of the photoelectric conversion film can be increased in the production process of the thin film compound solar cell, and as a result, the photoelectric conversion efficiency of the thin film compound solar cell can be increased.

また、本発明のガラス板は、少なくとも一方の表面に保護膜を有する。このようにすれば、ガラス板を保護することが可能になり、ガラス板に傷が付き難くなる。なお、本発明のガラス板は、一方の表面のみに保護膜を有する態様を含み、この場合、保護膜が形成された表面を運搬装置や搬送装置に接する側、或いは太陽光が照射される側にすればよい。   The glass plate of the present invention has a protective film on at least one surface. If it does in this way, it will become possible to protect a glass plate and it will become difficult to be damaged to a glass plate. In addition, the glass plate of this invention contains the aspect which has a protective film only in one surface, and in this case, the side which contact | connects the surface in which the protective film was formed to a conveying apparatus or a conveying apparatus, or the side irradiated with sunlight You can do it.

更に、本発明のガラス板は、保護膜がＳｒ含有硫酸塩及び／又はＢａ含有硫酸塩を含む。Ｓｒ含有硫酸塩とＢａ含有硫酸塩は、水の溶解度が非常に低い。よって、保護膜がＳｒ含有硫酸塩及び／又はＢａ含有硫酸塩を含むと、室温の水で洗浄した後でも、保護膜が消失し難くなる。結果として、長期に亘って、ガラス板に傷が付き難くなる。なお、Ｓｒ含有硫酸塩及び／又はＢａ含有硫酸塩を含む保護膜は、ガラス板の成形工程後、且つ徐冷炉投入前、或いはガラス板の洗浄工程後に形成されることが好ましい。   Furthermore, in the glass plate of the present invention, the protective film contains Sr-containing sulfate and / or Ba-containing sulfate. Sr-containing sulfate and Ba-containing sulfate have very low water solubility. Therefore, when the protective film contains Sr-containing sulfate and / or Ba-containing sulfate, the protective film is difficult to disappear even after washing with room temperature water. As a result, the glass plate is hardly damaged over a long period of time. The protective film containing Sr-containing sulfate and / or Ba-containing sulfate is preferably formed after the glass plate forming step and before the slow cooling furnace is charged, or after the glass plate cleaning step.

本発明のガラス板は、歪点が５６０℃以上であることが好ましい。   The glass plate of the present invention preferably has a strain point of 560 ° C. or higher.

本発明のガラス板は、保護膜が、亜硫酸ガスの吹き付けにより形成されてなることが好ましい。   In the glass plate of the present invention, the protective film is preferably formed by spraying sulfurous acid gas.

本発明のガラス板は、ガラス組成として、質量％で、ＳｉＯ２ ４０〜７０％、Ａｌ２Ｏ３ ６〜２０％、Ｂ２Ｏ３ ０〜１．５％、Ｎａ２Ｏ＋Ｋ２Ｏ ５〜３０％、Ｎａ２Ｏ ５〜２０％、ＳｒＯ＋ＢａＯ １０〜４０％を含有する。上記のように、各成分の含有量を限定した理由を下記に示す。 The glass plate of the present invention has a glass composition, in mass%, SiO 2 40~70%, Al 2 O 3 6~20%, B 2 O 3 0~1.5%, Na 2 O + K 2 O 5 ~30 %, Na 2 O 5 ~20% , containing SrO + BaO 10 ~40%. The reason for limiting the content of each component as described above is shown below.

ＳｉＯ２は、ガラスネットワークを形成する成分である。ＳｉＯ２の含有量は４０〜７０％、好ましくは４５〜６０％、より好ましくは４７〜５７％である。ＳｉＯ２の含有量が多過ぎると、高温粘度が不当に高くなり、溶融性、成形性が低下し易くなることに加えて、熱膨張係数が低くなり過ぎて、太陽電池の電極膜、光電変換膜の熱膨張係数に整合させ難くなる。一方、ＳｉＯ２の含有量が少な過ぎると、耐失透性が低下し易くなる。更に、熱膨張係数が高くなり過ぎて、ガラス板の耐熱衝撃性が低下し易くなり、結果として、太陽電池を製造する際の熱処理工程で、ガラス板に割れが発生し易くなる。 SiO 2 is a component that forms a glass network. The content of SiO 2 is 40 to 70%, preferably 45 to 60%, more preferably 47 to 57%. If the SiO 2 content is too large, the high-temperature viscosity becomes unduly high, the meltability and moldability tend to decrease, and the thermal expansion coefficient becomes too low, so that the solar cell electrode film, photoelectric conversion It becomes difficult to match the thermal expansion coefficient of the film. On the other hand, if the content of SiO 2 is too small, devitrification resistance is liable to decrease. Furthermore, since the thermal expansion coefficient becomes too high, the thermal shock resistance of the glass plate tends to be lowered, and as a result, the glass plate is likely to be cracked in the heat treatment step when manufacturing the solar cell.

Ａｌ２Ｏ３は、耐候性、化学的耐久性を高める成分であると共に、歪点を高める成分である。更にはガラス板の表面硬度を高める成分である。Ａｌ２Ｏ３の含有量は６〜２０％、好ましくは６〜１７％、より好ましくは６〜１５％である。Ａｌ２Ｏ３の含有量が多過ぎると、高温粘度が不当に高くなり、溶融性、成形性が低下し易くなる。一方、Ａｌ２Ｏ３の含有量が少な過ぎると、耐候性、化学的耐久性が低下し易くなり、歪点も低下し易くなる。なお、ガラス板の表面硬度が高いと、ＣＩＳ系太陽電池のパターニングにおいて、光電変換膜を除去する工程で、ガラス板が破損し難くなる。 Al 2 O 3 is a component that increases weather resistance and chemical durability, and also increases the strain point. Furthermore, it is a component that increases the surface hardness of the glass plate. The content of Al 2 O 3 is 6 to 20%, preferably 6 to 17%, more preferably 6 to 15%. When the content of Al 2 O 3 is too large, the high temperature viscosity becomes unduly high, meltability, moldability tends to decrease. On the other hand, when the content of Al 2 O 3 is too small, weather resistance, it is liable to lower chemical durability, also the strain point tends to decrease. In addition, when the surface hardness of a glass plate is high, it will become difficult to damage a glass plate in the process of removing a photoelectric converting film in patterning of a CIS type solar cell.

Ｂ２Ｏ３は、高温粘度を低下させて、溶融性や成形性を高める成分であるが、歪点も低下させる成分であり、また溶融時の成分揮発に伴い、炉耐火物材料を消耗させる成分である。よって、Ｂ２Ｏ３の含有量は０〜１．５％、好ましくは０〜０．１％未満である。 B 2 O 3 is a component that lowers the high-temperature viscosity and improves meltability and moldability, but is also a component that lowers the strain point, and consumes the furnace refractory material as the component volatilizes during melting. It is an ingredient. Therefore, the content of B 2 O 3 is 0 to 1.5%, preferably 0 to less than 0.1%.

Ｎａ２Ｏ＋Ｋ２Ｏは、高温粘度を低下させて、溶融性や成形性を高める成分である。また、Ｎａ２Ｏ＋Ｋ２Ｏは、ＣＩＳ系太陽電池において、カルコパイライト結晶の成長に効果的な成分であり、光電変換効率を高めるために重要な成分である。Ｎａ２Ｏ＋Ｋ２Ｏの含有量は５〜３０％、５〜２０％、特に７〜１５％が好ましい。Ｎａ２Ｏ＋Ｋ２Ｏの含有量が多過ぎると、Ｎａ又はＫを含む保護膜が発生し易くなり、洗浄により保護膜が消失し易くなる。また歪点が低下し易くなる。一方、Ｎａ２Ｏ＋Ｋ２Ｏの含有量が少な過ぎると、上記効果を享受し難くなる。 Na 2 O + K 2 O is a component that lowers the high-temperature viscosity and improves the meltability and moldability. Na 2 O + K 2 O is an effective component for the growth of chalcopyrite crystals in a CIS solar cell, and is an important component for increasing the photoelectric conversion efficiency. The content of Na 2 O + K 2 O is preferably 5 to 30%, 5 to 20%, and particularly preferably 7 to 15%. When Na 2 O + K 2 O content is too large, the protective film are easily generated containing Na or K, the protective film by washing is apt to disappear. In addition, the strain point tends to decrease. On the other hand, when the content of Na 2 O + K 2 O is too small, it becomes difficult to enjoy the above-mentioned effects.

Ｎａ２Ｏは、高温粘度を低下させて、溶融性や成形性を高める成分である。また、Ｎａ２Ｏ＋Ｋ２Ｏは、ＣＩＳ系太陽電池において、カルコパイライト結晶の成長に効果的な成分であり、光電変換効率を高めるために重要な成分である。Ｎａ２Ｏの含有量は５〜２０％、特に５〜１５％が好ましい。Ｎａ２Ｏの含有量が多過ぎると、Ｎａを含む保護膜が発生し易くなり、洗浄により保護膜が消失し易くなる。また歪点が低下し易くなる。一方、Ｎａ２Ｏの含有量が少な過ぎると、上記効果を享受し難くなる。 Na 2 O is a component that lowers the high temperature viscosity and improves the meltability and moldability. Na 2 O + K 2 O is an effective component for the growth of chalcopyrite crystals in a CIS solar cell, and is an important component for increasing the photoelectric conversion efficiency. The content of Na 2 O is from 5 to 20%, particularly 5 to 15% are preferred. When the content of Na 2 O is too large, the protective film are easily generated containing Na, protective film by washing is apt to disappear. In addition, the strain point tends to decrease. On the other hand, if too small content of Na 2 O, is difficult to enjoy the above-mentioned effects.

Ｋ２Ｏは、高温粘度を低下させて、溶融性や成形性を高める成分である。また、Ｋ２Ｏは、ＣＩＳ系太陽電池において、カルコパイライト結晶の成長を促進して、光電変換効率を高める成分である。Ｋ２Ｏの含有量は０．１〜３０％、１〜２０％、特に３〜１５％が好ましい。Ｋ２Ｏの含有量が多過ぎると、Ｋを含む保護膜が発生し易くなり、洗浄により保護膜が消失し易くなる。また歪点が低下し易くなる。一方、Ｋ２Ｏの含有量が少な過ぎると、上記効果を享受し難くなる。 K 2 O is a component that lowers the high temperature viscosity and improves the meltability and moldability. K 2 O is a component that promotes the growth of chalcopyrite crystals and increases the photoelectric conversion efficiency in the CIS solar cell. The content of K 2 O is preferably 0.1 to 30%, 1 to 20%, particularly preferably 3 to 15%. When the content of K 2 O is too large, the protective film are easily generated containing K, protective film by washing is apt to disappear. In addition, the strain point tends to decrease. On the other hand, when the K 2 O content is too small, it becomes difficult to enjoy the above-mentioned effects.

ＳｒＯ＋ＢａＯは、保護膜を構成する成分であり、また歪点を高める成分であり、更に高温粘度を低下させる成分である。ＳｒＯ＋ＢａＯの含有量は１０〜４０％、好ましくは１０〜３５％、より好ましくは１５〜３０％である。ＳｒＯ＋ＢａＯの含有量が多過ぎると、耐失透性が低下し易くなり、また原料コストが高騰する。一方、ＳｒＯ＋ＢａＯの含有量が少な過ぎると、Ｓｒ含有硫酸塩及び／又はＢａ含有硫酸塩を含む保護膜を形成し難くなり、また高温粘度が高くなり過ぎる。 SrO + BaO is a component constituting the protective film, a component for increasing the strain point, and a component for further decreasing the high temperature viscosity. The content of SrO + BaO is 10 to 40%, preferably 10 to 35%, more preferably 15 to 30%. When there is too much content of SrO + BaO, devitrification resistance will fall easily and raw material cost will rise. On the other hand, when there is too little content of SrO + BaO, it will become difficult to form the protective film containing Sr containing sulfate and / or Ba containing sulfate, and high temperature viscosity will become high too much.

ＳｒＯは、保護膜を構成する成分であり、また歪点を高める成分であり、更に高温粘度を低下させる成分である。ＳｒＯの含有量は、好ましくは０〜２５％、より好ましくは１．５〜１６％、更に好ましくは３〜１２％である。ＳｒＯの含有量が多過ぎると、耐失透性が低下し易くなり、また原料コストが高騰する。一方、ＳｒＯの含有量が少な過ぎると、Ｓｒ含有硫酸塩を含む保護膜を形成し難くなり、また高温粘度が高くなり易い。   SrO is a component constituting the protective film, a component for increasing the strain point, and a component for further decreasing the high temperature viscosity. The SrO content is preferably 0 to 25%, more preferably 1.5 to 16%, and still more preferably 3 to 12%. When there is too much content of SrO, devitrification resistance will fall easily and raw material cost will rise. On the other hand, if the SrO content is too small, it is difficult to form a protective film containing a Sr-containing sulfate, and the high-temperature viscosity tends to be high.

ＢａＯは、保護膜を構成する成分であり、また歪点を高める成分であり、更に高温粘度を低下させる成分である。ＢａＯの含有量は、好ましくは０〜２５％、より好ましくは１．５〜１５％、更に好ましくは３〜９．９％である。ＢａＯの含有量が多過ぎると、耐失透性が低下し易くなり、また原料コストが高騰する。一方、ＢａＯの含有量が少な過ぎると、Ｂａ含有硫酸塩を含む保護膜を形成し難くなり、また高温粘度が高くなり易い。   BaO is a component constituting the protective film, a component for increasing the strain point, and a component for further decreasing the high temperature viscosity. The content of BaO is preferably 0 to 25%, more preferably 1.5 to 15%, and still more preferably 3 to 9.9%. When there is too much content of BaO, devitrification resistance will fall easily and raw material cost will rise. On the other hand, when there is too little content of BaO, it will become difficult to form the protective film containing Ba containing sulfate, and high temperature viscosity will become high easily.

上記成分以外に、例えば、以下の成分を添加してもよい。   In addition to the above components, for example, the following components may be added.

Ｌｉ２Ｏは、高温粘度を低下させて、溶融性や成形性を高める成分である。また、Ｌｉ２Ｏは、Ｎａ２ＯやＫ２Ｏと同様にして、ＣＩＳ系太陽電池において、カルコパイライト結晶の成長に効果的な成分である。しかし、Ｌｉ２Ｏの含有量が多過ぎると、Ｌｉを含む保護膜が発生し易くなり、洗浄により保護膜が消失し易くなる。また原料コストが高騰することに加えて、歪点が大幅に低下する虞がある。よって、Ｌｉ２Ｏの含有量は０〜１０％、０〜２％、特に０〜０．１％未満が好ましい。 Li 2 O is a component that increases the meltability and moldability by lowering the high-temperature viscosity. Further, Li 2 O is an effective component for the growth of chalcopyrite crystals in CIS solar cells in the same manner as Na 2 O and K 2 O. However, when the content of Li 2 O is too large, a protective film containing Li is easily generated, and the protective film is easily lost by cleaning. Moreover, in addition to the raw material cost rising, there is a possibility that the strain point is greatly lowered. Therefore, the content of Li 2 O is preferably 0 to 10%, 0 to 2%, particularly preferably less than 0 to 0.1%.

ＭｇＯ＋ＣａＯは、歪点を高める成分であり、また高温粘度を低下させて、溶融性や成形牲を高める成分である。ＭｇＯ＋ＣａＯの含有量は０〜３０％、０〜２０％、特に０〜１５％が好ましい。ここで、「ＭｇＯ＋ＣａＯ」は、ＭｇＯとＣａＯの合量である。   MgO + CaO is a component that increases the strain point, and also increases the meltability and moldability by reducing the high temperature viscosity. The content of MgO + CaO is preferably 0 to 30%, 0 to 20%, particularly preferably 0 to 15%. Here, “MgO + CaO” is the total amount of MgO and CaO.

ＭｇＯは、歪点を高める成分であり、また高温粘度を低下させて、溶融性や成形牲を高める成分である。ＭｇＯの含有量は０〜２５％、０〜１５％、特に０〜１０％が好ましい。   MgO is a component that increases the strain point, and also increases the meltability and moldability by reducing the high-temperature viscosity. The content of MgO is preferably 0 to 25%, 0 to 15%, particularly preferably 0 to 10%.

ＣａＯは、歪点を高める成分であり、また高温粘度を低下させて、溶融性や成形牲を高める成分である。ＣａＯの含有量は０〜２５％、０〜１５％、特に０〜１０％が好ましい。   CaO is a component that increases the strain point, and also increases the meltability and moldability by reducing the high temperature viscosity. The content of CaO is preferably 0 to 25%, 0 to 15%, particularly preferably 0 to 10%.

ＺｒＯ２は、高温粘度を上げずに、歪点を高める成分である。しかし、ＺｒＯ２の含有量が多過ぎると、失透し易くなり、ガラス板に成形し難くなる。よって、ＺｒＯ２の含有量は０〜１５％、０〜１０％、特に０〜７％が好ましい。 ZrO 2 is a component that increases the strain point without increasing the high-temperature viscosity. However, when the content of ZrO 2 is too large, easily devitrified, it becomes difficult to mold the glass sheet. Therefore, the content of ZrO 2 is preferably 0 to 15%, 0 to 10%, particularly preferably 0 to 7%.

上記成分以外にも、原料コストを低廉化するために、不純物としてＦｅ２Ｏ３を０．２％まで添加してもよい。紫外線による着色を防止するために、ＴｉＯ２を３％まで添加してもよい。耐失透性を高めるために、Ｐ２Ｏ５を３％まで添加してもよい。高温粘度を低下させるために、ＺｎＯを３％まで添加してもよい。清澄剤としてＳＯ３、Ｓｂ２Ｏ３、ＳｎＯ２、Ｆ、Ｃｌ、Ｂｒ等を合量で２％まで添加してもよい。 In addition to the above components, Fe 2 O 3 may be added up to 0.2% as an impurity in order to reduce the raw material cost. In order to prevent coloring due to ultraviolet rays, TiO 2 may be added up to 3%. In order to improve devitrification resistance, P 2 O 5 may be added up to 3%. In order to reduce the high temperature viscosity, ZnO may be added up to 3%. As a clarifier, SO 3 , Sb 2 O 3 , SnO 2 , F, Cl, Br, etc. may be added up to 2% in total.

本発明のガラス板は、保護膜がＳｒ含有硫酸塩及び／又はＢａ含有硫酸塩を含むことを特徴とする。Ｓｒ含有硫酸塩とＢａ含有硫酸塩は、水の溶解度が非常に低い。よって、保護膜がＳｒ含有硫酸塩及び／又はＢａ含有硫酸塩を含むと、室温の水で洗浄した後でも、保護膜が消失し難くなる。結果として、長期に亘って、ガラス板に傷が付き難くなる。なお、上記保護膜の形成方法は、特に限定されず、ガラス板の表面に亜硫酸ガスを吹き付ける方法、ガラス板の表面をスラリーコートした後に焼成する方法等を採用することができる。   The glass plate of the present invention is characterized in that the protective film contains Sr-containing sulfate and / or Ba-containing sulfate. Sr-containing sulfate and Ba-containing sulfate have very low water solubility. Therefore, when the protective film contains Sr-containing sulfate and / or Ba-containing sulfate, the protective film is difficult to disappear even after washing with room temperature water. As a result, the glass plate is hardly damaged over a long period of time. In addition, the formation method of the said protective film is not specifically limited, The method of spraying a sulfurous acid gas on the surface of a glass plate, the method of baking after slurry-coating the surface of a glass plate, etc. are employable.

本発明のガラス板において、歪点は、好ましくは５６０℃以上、５８０〜６５０℃、６００超〜６４０℃、特に６１０〜６３０℃である。このようにすれば、太陽電池を製造する際の熱処理工程で、ガラス板に熱収縮や熱変形が生じ難くなる。   In the glass plate of the present invention, the strain point is preferably 560 ° C. or higher, 580 to 650 ° C., more than 600 to 640 ° C., particularly 610 to 630 ° C. If it does in this way, it will become difficult to produce thermal contraction and thermal deformation to a glass plate at the heat treatment process at the time of manufacturing a solar cell.

本発明のガラス板は、化学強化処理、特にイオン交換処理が行われていないことが好ましい。特に、薄膜化合物太陽電池には、高温の成膜工程が存在する。よって、化学強化処理により圧縮応力層を形成しても、この工程で、強化層（圧縮応力層）が消失し、化学強化処理を行う実益が乏しくなる。更に、ＣＩＳ系太陽電池の場合、ガラス板をイオン交換処理すると、ガラス表面のＮａイオンが減少してしまい、光電変換効率が低下し易くなる。   The glass plate of the present invention is preferably not subjected to chemical strengthening treatment, particularly ion exchange treatment. In particular, a thin film compound solar cell has a high temperature film forming process. Therefore, even if the compressive stress layer is formed by the chemical strengthening treatment, the strengthening layer (compressive stress layer) disappears in this step, and the actual benefit of performing the chemical strengthening treatment becomes poor. Furthermore, in the case of a CIS solar cell, when the glass plate is subjected to ion exchange treatment, Na ions on the glass surface are reduced, and the photoelectric conversion efficiency is likely to be lowered.

本発明のガラス板は、上記のガラス組成範囲になるように、調合したガラス原料を連続溶融炉に投入し、ガラス原料を加熱溶融した後、得られたガラス融液を脱泡した上で、成形装置に供給し、ガラス板に成形、徐冷することにより、作製することができる。ガラス板の成形方法として、フロート法、スロットダウンドロー法、オーバーフローダウンドロー法、リドロー法等が挙げられる。   The glass plate of the present invention is charged with the prepared glass raw material in a continuous melting furnace so as to be in the above glass composition range, and after the glass raw material is heated and melted, after defoaming the obtained glass melt, It can be produced by supplying to a molding apparatus, molding into a glass plate and slow cooling. Examples of the glass plate forming method include a float method, a slot down draw method, an overflow down draw method, and a redraw method.

特に、ガラス板の成形方法として、フロート法が好ましい。このようにすれば、大型のガラス板を安価、且つ大量に製造することができる。また、このようにすれば、成形工程後、且つ徐冷炉投入前のガラス板の表面に亜硫酸ガスを吹き付けることにより、容易に保護膜を形成することができる。   In particular, the float method is preferable as a method for forming the glass plate. If it does in this way, a large sized glass plate can be manufactured cheaply and in large quantities. Moreover, if it does in this way, a protective film can be easily formed by spraying a sulfurous acid gas on the surface of the glass plate after a shaping | molding process and before charging a slow cooling furnace.

以下、実施例に基づいて、本発明を詳細に説明する。なお、以下の実施例は単なる例示である。本発明は、以下の実施例に何ら限定されない。   Hereinafter, based on an Example, this invention is demonstrated in detail. The following examples are merely illustrative. The present invention is not limited to the following examples.

表１は、試料Ｎｏ．１〜４を示している。   Table 1 shows Sample No. 1 to 4 are shown.

次のようにして、試料Ｎｏ．１〜４を作製した。まず表中のガラス組成になるように調合したガラスバッチを白金坩堝に入れ、１５５０℃で２時間溶融した。次に、得られた溶融ガラスをカーボン板上に流し出して、ガラス板に成形した後、徐冷した。その後、各測定に応じて、所定の加工を行った。得られた各試料について、歪点Ｐｓ、保護膜消失の有無を評価した。これらの結果を表１に示す。   Sample no. 1-4 were produced. First, a glass batch prepared so as to have the glass composition in the table was placed in a platinum crucible and melted at 1550 ° C. for 2 hours. Next, the obtained molten glass was poured onto a carbon plate, formed into a glass plate, and then slowly cooled. Thereafter, predetermined processing was performed according to each measurement. About each obtained sample, the strain point Ps and the presence or absence of a protective film disappearance were evaluated. These results are shown in Table 1.

歪点Ｐｓは、ＡＳＴＭ Ｃ３３６−７１に基づいて測定した値である。   The strain point Ps is a value measured based on ASTM C336-71.

次のようにして、保護膜消失の有無を評価した。まずガラス板の一方の表面に対して、ＳＯ２ガスを６５０℃で５分間吹き付けた後、室温の水で洗浄した。次に、ガラス板の一方の表面に保護膜が残存しているかを確認した。 The presence or absence of protective film disappearance was evaluated as follows. First, SO 2 gas was sprayed at 650 ° C. for 5 minutes on one surface of the glass plate, and then washed with water at room temperature. Next, it was confirmed whether the protective film remained on one surface of the glass plate.

表１から明らかなように、試料Ｎｏ．１〜３は、室温の水で洗浄した後も保護膜（Ｓｒ含有硫酸塩及びＢａ含有硫酸塩）が残存していた。更に、試料Ｎｏ．１〜３は、歪点Ｐｓが５８０〜６３０℃であるため、高い耐熱性を有している。一方、試料Ｎｏ．４は、ガラス組成中にＳｒＯとＢａＯを含んでいないため、ＳＯ２ガスの吹き付けによりＳｒ含有硫酸塩及び／又はＢａ含有硫酸塩が生成せず、室温の水で洗浄した後に保護膜が消失していた。 As is clear from Table 1, sample No. In Nos. 1 to 3, the protective films (Sr-containing sulfate and Ba-containing sulfate) remained after washing with water at room temperature. Furthermore, sample no. 1 to 3 have high heat resistance because the strain point Ps is 580 to 630 ° C. On the other hand, sample No. No. 4 does not contain SrO and BaO in the glass composition, so Sr-containing sulfate and / or Ba-containing sulfate is not generated by blowing SO 2 gas, and the protective film disappears after washing with water at room temperature. It was.

Claims (2)

少なくとも一方の表面に保護膜を有するガラス板において、
ガラス組成として、質量％で、ＳｉＯ２ ４０〜７０％、Ａｌ２Ｏ３ ６〜２０％、Ｂ２Ｏ３ ０〜１．５％、Ｎａ２Ｏ＋Ｋ２Ｏ ５〜３０％、Ｎａ２Ｏ ５〜２０％、ＳｒＯ＋ＢａＯ １０〜４０％を含有し、保護膜がＳｒ含有硫酸塩及び／又はＢａ含有硫酸塩を含み、且つ薄膜化合物太陽電池に用いることを特徴とするガラス板。 In a glass plate having a protective film on at least one surface,
As a glass composition, in mass%, SiO 2 40~70%, Al 2 O 3 6~20%, B 2 O 3 0~1.5%, Na 2 O + K 2 O 5 ~30%, Na 2 O 5 ~ 20%, contains SrO + BaO 10 to 40% glass plate coercive Mamorumaku is seen containing a Sr-containing sulfates and / or Ba-containing sulfates and is characterized by using the thin-film compound solar cell. 歪点が５６０℃以上であることを特徴とする請求項１に記載のガラス板。   The glass plate according to claim 1, wherein the strain point is 560 ° C. or higher.
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