JP2009117436A - Solar energy utilizing device, and manufacturing method thereof - Google Patents
Solar energy utilizing device, and manufacturing method thereof Download PDFInfo
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- JP2009117436A JP2009117436A JP2007285770A JP2007285770A JP2009117436A JP 2009117436 A JP2009117436 A JP 2009117436A JP 2007285770 A JP2007285770 A JP 2007285770A JP 2007285770 A JP2007285770 A JP 2007285770A JP 2009117436 A JP2009117436 A JP 2009117436A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
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- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000005871 repellent Substances 0.000 claims abstract description 38
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 34
- 230000002940 repellent Effects 0.000 claims abstract description 32
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 25
- 239000000126 substance Substances 0.000 claims description 184
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 89
- 239000011737 fluorine Substances 0.000 claims description 72
- 229910052731 fluorine Inorganic materials 0.000 claims description 72
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 71
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- 239000005046 Chlorosilane Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 238000009835 boiling Methods 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
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- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
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- 239000011356 non-aqueous organic solvent Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
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- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- NVSXSBBVEDNGPY-UHFFFAOYSA-N 1,1,1,2,2-pentafluorobutane Chemical compound CCC(F)(F)C(F)(F)F NVSXSBBVEDNGPY-UHFFFAOYSA-N 0.000 description 1
- CJAGRJAFLCPABV-UHFFFAOYSA-N 2-(4-methylpentan-2-ylideneamino)-n-[2-(4-methylpentan-2-ylideneamino)ethyl]ethanamine Chemical compound CC(C)CC(C)=NCCNCCN=C(C)CC(C)C CJAGRJAFLCPABV-UHFFFAOYSA-N 0.000 description 1
- NOJHYEMRGGBHOI-UHFFFAOYSA-N 2-(butan-2-ylideneamino)-n-[2-(butan-2-ylideneamino)ethyl]ethanamine Chemical compound CCC(C)=NCCNCCN=C(C)CC NOJHYEMRGGBHOI-UHFFFAOYSA-N 0.000 description 1
- CLSFJOSFPTTYLQ-UHFFFAOYSA-N 2-(methylideneamino)-n-[2-(methylideneamino)ethyl]ethanamine Chemical compound C=NCCNCCN=C CLSFJOSFPTTYLQ-UHFFFAOYSA-N 0.000 description 1
- FPHDXPRLWRPJNS-UHFFFAOYSA-N 2-(propan-2-ylideneamino)-n-[2-(propan-2-ylideneamino)ethyl]ethanamine Chemical compound CC(C)=NCCNCCN=C(C)C FPHDXPRLWRPJNS-UHFFFAOYSA-N 0.000 description 1
- MMGVVYCBXBYXRR-UHFFFAOYSA-L 2-acetyl-3-oxobutanoate;dibutyltin(2+) Chemical compound CCCC[Sn+2]CCCC.CC(=O)C(C(C)=O)C([O-])=O.CC(=O)C(C(C)=O)C([O-])=O MMGVVYCBXBYXRR-UHFFFAOYSA-L 0.000 description 1
- ZHJFAUWFPQHZFH-UHFFFAOYSA-L 2-ethylhex-2-enoate iron(2+) Chemical compound [Fe+2].CCCC=C(CC)C([O-])=O.CCCC=C(CC)C([O-])=O ZHJFAUWFPQHZFH-UHFFFAOYSA-L 0.000 description 1
- COAUHYBSXMIJDK-UHFFFAOYSA-N 3,3-dichloro-1,1,1,2,2-pentafluoropropane Chemical compound FC(F)(F)C(F)(F)C(Cl)Cl COAUHYBSXMIJDK-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- QASXJOGGAHCHBO-UHFFFAOYSA-L [dimethyl(2-sulfanylpropanoyloxy)stannyl] 2-sulfanylpropanoate Chemical compound C[Sn+2]C.CC(S)C([O-])=O.CC(S)C([O-])=O QASXJOGGAHCHBO-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DKCFPRIRHWNCIX-UHFFFAOYSA-L dioctyltin(2+);2-octyl-2-sulfanyldecanoate Chemical compound CCCCCCCC[Sn+2]CCCCCCCC.CCCCCCCCC(S)(C([O-])=O)CCCCCCCC.CCCCCCCCC(S)(C([O-])=O)CCCCCCCC DKCFPRIRHWNCIX-UHFFFAOYSA-L 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 150000004658 ketimines Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
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- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
-
- 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
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- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
本発明は、高耐久性の撥水撥油防汚性被膜が表面に形成された太陽エネルギー利用装置に関するものである。具体的には、撥水撥油防汚機能が要求される太陽電池パネルや太陽熱温水器、温室に関するものである。 The present invention relates to a solar energy utilization device having a highly durable water / oil repellent / antifouling coating formed on the surface thereof. Specifically, the present invention relates to a solar cell panel, a solar water heater, and a greenhouse that require a water / oil repellent / antifouling function.
一般にフッ化炭素基含有クロロシラン系の吸着剤と非水系の有機溶媒よりなる化学吸着液を用い、液相で化学吸着して単分子膜状の撥水撥油防汚性化学吸着膜を形成できることはすでによく知られている（例えば、特許文献１参照。）。 In general, a chemical adsorption solution consisting of a fluorocarbon group-containing chlorosilane-based adsorbent and a non-aqueous organic solvent can be used for chemical adsorption in the liquid phase to form a monomolecular film-like water / oil repellent / antifouling chemical adsorption film. Is already well known (for example, see Patent Document 1).
このような溶液中での化学吸着単分子膜の製造原理は、基材表面の水酸基などの活性水素とクロロシラン系の吸着剤のクロロシリル基との脱塩酸反応を用いて単分子膜を形成することにある。
しかしながら、従来の化学吸着膜は吸着剤と基材表面との化学結合のみを用いているため、太陽エネルギー利用装置の防汚離水膜として用いた場合には、耐摩耗性等の耐久性が乏しいという課題があった。また、クロロシラン系界面活性剤を用いた方法では、製膜時に塩酸が発生するため、製造は、特別な脱塩酸設備を備えた隔離された場所で行わなければならないという課題があった。 However, since the conventional chemical adsorption film uses only the chemical bond between the adsorbent and the substrate surface, when it is used as an antifouling water separation film of a solar energy utilization device, durability such as wear resistance is poor. There was a problem. Further, in the method using a chlorosilane-based surfactant, hydrochloric acid is generated during film formation, and thus there is a problem that the production must be performed in an isolated place equipped with a special dehydrochlorination facility.
本発明は、撥水撥油防汚機能が要求される太陽エネルギー利用装置において、受光面側最表面の耐摩耗性および耐候性等の耐久性、雨滴離水性（滑水性ともいう）、防汚性の向上を目的とする。また、最表面に撥水撥油防汚膜を形成する際、塩酸を発生させずに（あるいはほんの少量の塩酸の発生で）、耐摩耗性および耐候性等の耐久性、および雨滴離水性（滑水性ともいう）、防汚性に優れた被膜を形成することを目的とする。 The present invention relates to a solar energy utilization device that requires a water / oil repellent / antifouling function, durability such as wear resistance and weather resistance of the outermost surface of the light receiving surface, raindrop water separation (also referred to as water slidability), and antifouling. The purpose is to improve performance. In addition, when forming a water and oil repellent antifouling film on the outermost surface, without generating hydrochloric acid (or by generating only a small amount of hydrochloric acid), durability such as wear resistance and weather resistance, and raindrop water separation ( The purpose is to form a film excellent in antifouling property.
前記課題を解決するための手段として提供される第１の発明は、受光面側最表面に、高耐久性の撥水撥油防汚性被膜が形成されたガラス板であって、前記被膜が、フッ化炭素基と炭化水素基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質を含む複合膜が形成されていることを特徴とする太陽エネルギー利用装置である。 A first invention provided as a means for solving the above problems is a glass plate in which a highly durable water / oil / oil repellent film is formed on the outermost surface of the light receiving surface. , A composite film containing a long-chain material mainly composed of a fluorocarbon group and a hydrocarbon group, a short-chain material mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group, and a material mainly composed of a siloxane group Is a solar energy utilization device characterized by being formed.
第２の発明は、第１の発明に於いて、フッ化炭素基と炭化水素基を主成分とする長鎖物質の分子長がフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質の分子長の２倍以上であることを特徴とする太陽エネルギー利用装置である。 According to a second invention, in the first invention, the molecular length of a long-chain substance mainly composed of a fluorocarbon group and a hydrocarbon group is composed mainly of a fluorocarbon group, a hydrocarbon group and a silyl group. It is a solar energy utilization apparatus characterized by being more than twice the molecular length of a short chain substance.
第３の発明は、第１および２の発明に於いて、フッ化炭素基と炭化水素基を主成分とする長鎖物質がフッ化炭素基と炭化水素基を含む側鎖を持っていることを特徴とする太陽エネルギー利用装置である。 According to a third invention, in the first and second inventions, the long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group has a side chain containing the fluorocarbon group and the hydrocarbon group. It is a solar energy utilization apparatus characterized by this.
第４の発明は、第１乃至３の発明に於いて、フッ化炭素基と炭化水素基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質が、シロキサン基を主成分とする物質よりなるシリカ膜中で前記シリル基を介して前記シリカ膜および／またはガラス板表面に結合固定されていることを特徴とする太陽エネルギー利用装置である。 According to a fourth aspect of the present invention, in the first to third aspects of the present invention, a short-chain material mainly composed of a fluorocarbon group and a hydrocarbon group, a short chain composed mainly of a fluorocarbon group, a hydrocarbon group, and a silyl group. A solar energy utilization apparatus characterized in that a chain substance is bonded and fixed to the silica film and / or the glass plate surface via the silyl group in a silica film made of a substance mainly composed of a siloxane group. .
第５の発明は、第１乃至４の発明に於いて、フッ化炭素基と炭化水素基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質が、それぞれシリル基およびシロキサン基を介して互いにまたは個々にガラス板表面に結合固定されていることを特徴とする太陽エネルギー利用装置である。 According to a fifth aspect of the present invention, in the first to fourth aspects of the present invention, a long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group, a short chain composed mainly of a fluorocarbon group, a hydrocarbon group, and a silyl group. The solar energy utilization apparatus is characterized in that a chain substance and a substance mainly composed of a siloxane group are bonded to each other or individually on the glass plate surface via a silyl group and a siloxane group, respectively.
第６の発明は、第１乃至５の発明に於いて、撥水撥油防汚性被膜に含まれるフッ化炭素基と炭化水素基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質の分子組成比が、１：１０：１０〜１：０：０であることを特徴とするに記載の太陽エネルギー利用装置である。
According to a sixth invention, in the first to fifth inventions, a long-chain material mainly comprising a fluorocarbon group and a hydrocarbon group, a fluorocarbon group, and a carbonization contained in the water / oil repellent / antifouling coating. The solar composition according to
第７の発明は、第１乃至６の発明に於いて、表面に撥水撥油防汚性被膜が形成されたガラス板であって、前記被膜が、少なくともフッ化炭素基と炭化水素基を主成分とする長鎖物質を含み前記被膜の臨界表面エネルギーが５〜２０ｍＮ／ｍに制御されていることを特徴とする太陽エネルギー利用装置である。 A seventh invention is the glass plate according to any one of the first to sixth inventions, wherein a water repellent and oil repellent antifouling coating is formed on the surface, wherein the coating contains at least a fluorocarbon group and a hydrocarbon group. It is a solar energy utilization apparatus characterized by including the long-chain substance which is a main component, and the critical surface energy of the said film being controlled to 5-20 mN / m.
第８の発明は、第１乃至７の発明に於いて、フッ化炭素基と炭化水素基を主成分とする長鎖物質が有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質であることを特徴とする太陽エネルギー利用装置である。 According to an eighth invention, in the first to seventh inventions, the long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group is composed mainly of an organic fluorine-containing ether group or an organic fluorine-containing polyether group. It is a solar energy utilization device characterized by being a long chain substance.
第９の発明は、第１乃至８の発明に於いて、有機含フッ素エーテル基または有機含フッ素ポリエーテル基が下記式（化１または化２）に示した官能基であることを特徴とする太陽エネルギー利用装置である。
第１０の発明は、第１乃至９の発明に於いて、撥水撥油防汚性被膜がアルカリバリア膜を介して形成されていることを特徴とする太陽エネルギー利用装置である。 A tenth invention is the solar energy utilization device according to any one of the first to ninth inventions, wherein the water- and oil-repellent and antifouling coating is formed through an alkali barrier film.
第１１の発明は、第１乃至１０の発明に於いて、複合膜がさらにメチルシリル基を含んでいることを特徴とする太陽エネルギー利用装置である。 An eleventh invention is the solar energy utilization device according to any one of the first to tenth inventions, wherein the composite film further contains a methylsilyl group.
第１２の発明は、少なくとも受光面側最表面に、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)とシラノール縮合触媒とを有機溶媒で希釈した複合膜形成溶液を接触、反応させ撥水撥油防汚性の複合膜を形成する工程を含むことを特徴とする太陽エネルギー利用装置の製造方法である。 According to a twelfth aspect of the present invention, there is provided a long-chain substance (1) comprising a fluorocarbon group and a hydrocarbon group as main components and containing an alkoxysilyl group, a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl, Water- and oil-repellent and anti-repellent properties by contacting and reacting a short-chain substance (2) containing a group as a main component, a substance (3) containing an alkoxysilyl group as a main component and a silanol condensation catalyst diluted with an organic solvent. It is a manufacturing method of the solar energy utilization apparatus characterized by including the process of forming a dirty composite film.
第１３の発明は、少なくとも受光面側最表面に、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)とシラノール縮合触媒とを有機溶媒で希釈した複合膜形成溶液を接触、反応させ撥水撥油防汚性の複合膜を形成する工程と、前記ガラス板表面の余分な溶液を有機溶媒を用いて洗浄除去またはふき取り除去する工程とを含むことを特徴とする太陽エネルギー利用装置の製造方法である。 According to a thirteenth aspect of the present invention, there is provided a long-chain substance (1) comprising a fluorocarbon group and a hydrocarbon group as main components and containing an alkoxysilyl group, a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl, Water- and oil-repellent and anti-repellent properties by contacting and reacting a short-chain substance (2) based on a group, a substance (3) based on an alkoxysilyl group and a silanol condensation catalyst diluted with an organic solvent. A method for manufacturing a solar energy utilization device, comprising: a step of forming a dirty composite film; and a step of washing or wiping off an excess solution on the surface of the glass plate using an organic solvent.
第１４の発明は、第１２および１３の発明に於いて、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)の分子混合比を、１：１０：１０〜１：０：０にしておくことを特徴とする太陽エネルギー利用装置の製造方法である。 A fourteenth invention is the twelfth and thirteenth invention according to the twelfth and thirteenth inventions, a long-chain substance (1) comprising a fluorocarbon group and a hydrocarbon group as main components and an alkoxysilyl group, a fluorocarbon group and a hydrocarbon group, and The molecular mixing ratio of the short chain substance (2) mainly composed of an alkoxysilyl group and the substance (3) mainly composed of an alkoxysilyl group is set to 1:10:10 to 1: 0: 0. It is a manufacturing method of the solar energy utilization apparatus.
第１５の発明は、第１２乃至１４の発明に於いて、少なくともフッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)として有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質を用いることを特徴とする太陽エネルギー利用装置の製造方法である。 According to a fifteenth aspect, in the twelfth to fourteenth aspects, the organic fluorine-containing ether group or the organic group-containing substance is used as the long-chain substance (1) comprising at least a fluorocarbon group and a hydrocarbon group as main components and an alkoxysilyl group. A method for producing a solar energy utilization device, characterized in that a long chain material containing a fluorine polyether group and an alkoxysilyl group is used.
第１６の発明は、第１５の発明に於いて、有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質として下記式（化３または化４）に示した物質を用い、
フッ化炭素基と炭化水素基とアルコキシシリル基を主成分とする短鎖物質(2)としてＣＦ3−（ＣＦ2）ｏ−（ＣＨ２）２−Ｓｉ（ＯＡ）3、またはＣＦ3−（ＣＦ2）ｏ−（ＣＨ２）２−ＳｉＣＨ3（ＯＡ）２（添え字のｏは整数、Ａはアルキル基、ＯＡはＣｌまたはＮＣＯでも良い。ただし、Ｃｌをもちいれば、製膜工程で塩酸が発生する。）を用い、アルコキシシリルキ基を主成分とする物質(3)として（ＡＯ）３Ｓｉ（ＯＳｉ（ＯＡ）２）ｐＯＡ（ｐは０または整数、Ａはアルキル基、ＯＡはＣｌまたはＮＣＯでも良い。ただし、Ｃｌをもちいれば、製膜工程で塩酸が発生する。）を用いることを特徴とする太陽エネルギー利用装置の製造方法である。 CF 3 — (CF 2 ) o — (CH 2 ) 2 —Si (OA) 3 , or CF 3 — () as a short chain substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. CF 2 ) o — (CH 2 ) 2 —SiCH 3 (OA) 2 (The subscript o is an integer, A is an alkyl group, and OA may be Cl or NCO. However, if Cl is used, in the film forming step, (AO) 3 Si (OSi (OA) 2 ) p OA (p is 0 or an integer, A is an alkyl group, OA) May be Cl or NCO (however, if Cl is used, hydrochloric acid is generated in the film-forming process), this is a method for manufacturing a solar energy utilization device.
第１７の発明は、第１５の発明に於いて、有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質として、下記式（化５）に示した物質を用い、
フッ化炭素基と炭化水素基とアルコキシシリル基を主成分とする短鎖物質(2)としてＣＦ3−（ＣＦ2）ｏ−（ＣＨ２）２−Ｓｉ（ＯＡ）3（添え字のｏは整数、Ａはアルキル基。）を用い、アルコキシシリルキ基を主成分とする物質(3)として（ＡＯ）３Ｓｉ（ＯＳｉ（ＯＡ）２）ｐＯＡ（Ｐは０または整数、Ａはアルキル基。）を用いることを特徴とする太陽エネルギー利用装置の製造方法である。 CF 3 — (CF 2 ) o — (CH 2 ) 2 —Si (OA) 3 (subscript o is a short chain substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. (AO) 3 Si (OSi (OA) 2 ) p OA (P is 0 or an integer, A is an alkyl group) .) Is used to manufacture a solar energy utilization device.
第１８の発明は、第１２乃至１７の発明に於いて、シラノール縮合触媒の代わりに、ケチミン化合物、又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物、あるいはＴｉＯ２等の金属酸化物を用いることを特徴とする太陽エネルギー利用装置の製造方法である。 An eighteenth invention is the twelfth to seventeenth invention, in which instead of the silanol condensation catalyst, a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, an aminoalkylalkoxysilane compound, or TiO 2 is used. It is a manufacturing method of the solar energy utilization apparatus characterized by using a metal oxide.
第１９の発明は、第１２乃至１７の発明に於いて、シラノール縮合触媒にケチミン化合物、又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物および／あるいはＴｉＯ２等の金属酸化物を混合して用いることを特徴とする太陽エネルギー利用装置の製造方法である。 According to a nineteenth aspect, in the twelfth to seventeenth aspects, the silanol condensation catalyst includes a ketimine compound, or a metal oxide such as an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, an aminoalkylalkoxysilane compound and / or TiO 2. It is a manufacturing method of the solar energy utilization apparatus characterized by using a thing mixed.
第２０の発明は、第１２乃至１９の発明に於いて、有機溶媒としてフッ化炭素系有機溶媒を用いることを特徴とする太陽エネルギー利用装置の製造方法である。 A twentieth aspect of the invention is a method for manufacturing a solar energy utilization device according to the twelfth to nineteenth aspects of the invention, wherein a fluorocarbon organic solvent is used as the organic solvent.
第２１の発明は、第１２乃至２０の発明に於いて、複合膜形成前にあらかじめガラス板表面にアルカリバリア膜としてシリカ膜を形成しておくことを特徴とする太陽エネルギー利用装置の製造方法である。 A twenty-first invention is a method for manufacturing a solar energy utilization device according to any of the twelfth to twentieth inventions, wherein a silica film is formed as an alkali barrier film on the glass plate surface in advance before forming the composite film. is there.
第２２の発明は、第１２乃至２１の発明に於いて、複合膜形成後、２５０〜４５０℃で加熱することを特徴とする太陽エネルギー利用装置の製造方法である。 A twenty-second invention is a method for manufacturing a solar energy utilization device according to the twelfth to twenty-first invention, wherein the composite film is heated at 250 to 450 ° C.
第２３の発明は、第１２乃至２１の発明に於いて、複合膜形成後、さらにメチルシリル基を含んだ物質を溶かした溶液で処理することを特徴とする太陽エネルギー利用装置の製造方法である。 A twenty-third aspect of the invention is a method for manufacturing a solar energy utilization device according to the twelfth to twenty-first aspects of the invention, wherein after the formation of the composite film, treatment is performed with a solution in which a substance containing a methylsilyl group is further dissolved.
さらに具体的説明すると、本発明は、少なくとも受光面側最表面に、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)とシラノール縮合触媒とを有機溶媒で希釈した複合膜形成溶液を接触、反応させ撥水撥油防汚性の複合膜を形成する工程とにより、あるいは、少なくとも受光面側最表面に、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)とシラノール縮合触媒とを有機溶媒で希釈した複合膜形成溶液を接触、反応させ撥水撥油防汚性の複合膜を形成する工程と、前記ガラス板表面の余分な溶液を有機溶媒を用いて洗浄除去またはふき取り除去する工程とにより、受光面側最表面に、高耐久性の撥水撥油防汚性被膜が形成された太陽エネルギー利用装置であって、前記被膜が、フッ化炭素基と炭化水素基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質を含む複合膜であることを特徴とする太陽エネルギー利用装置を製造して提供するものである。 More specifically, the present invention relates to a long-chain substance (1) comprising at least a fluorocarbon group and a hydrocarbon group as main components and an alkoxysilyl group, and a fluorocarbon group and a hydrocarbon. A composite film forming solution obtained by diluting a silanol condensation catalyst with a short chain substance (2) having an alkoxy group and an alkoxysilyl group as a main component, a substance (3) having an alkoxysilyl group as a main component and a silanol condensation catalyst in contact with each other and reacting A long-chain material comprising a fluorocarbon group and a hydrocarbon group as main components and an alkoxysilyl group at least on the outermost surface on the light-receiving surface side, by a step of forming a water / oil repellent / antifouling composite film (1) A short-chain substance (2) mainly composed of fluorocarbon groups, hydrocarbon groups and alkoxysilyl groups (2), a substance mainly composed of alkoxysilyl groups (3) and a silanol condensation catalyst diluted with an organic solvent Contact the forming solution, And a step of forming a composite film having water and oil repellent and antifouling properties and a step of washing or wiping off the excess solution on the surface of the glass plate with an organic solvent. A solar energy utilization device having a durable water / oil repellent / antifouling coating formed thereon, wherein the coating comprises a long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group, a fluorocarbon group, and a carbonization. The present invention manufactures and provides a solar energy utilization device, which is a composite film including a short chain material mainly composed of a hydrogen group and a silyl group and a material mainly composed of a siloxane group.
ここで、フッ化炭素基と炭化水素基を主成分とする長鎖物質の分子長がフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質の分子長の２倍以上であると、複合膜の耐久性と雨滴離水性（滑水性とも言う。）を同時に向上できて好都合である。 Here, the molecular length of a long-chain substance mainly composed of a fluorocarbon group and a hydrocarbon group is more than twice the molecular length of a short-chain substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group. The advantage is that the durability of the composite film and raindrop water separation (also referred to as water slidability) can be improved at the same time.
また、フッ化炭素基と炭化水素基を主成分とする長鎖物質がフッ化炭素基と炭化水素基を含む側鎖を持っていると、より一層複合膜の耐久性と雨滴離水性を同時に向上できて好都合である。 In addition, if a long-chain material mainly composed of a fluorocarbon group and a hydrocarbon group has a side chain containing a fluorocarbon group and a hydrocarbon group, the durability of the composite membrane and raindrop water separation can be further improved. It is convenient to improve.
さらに、フッ化炭素基と炭化水素基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質が、シロキサン基を主成分とする物質よりなるシリカ膜中で前記シリル基を介して前記シリカ膜および／またはガラス板表面に結合固定されていると、耐候性を向上する上で都合がよい。 Further, a long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group and a short chain substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group are composed of a substance mainly composed of a siloxane group. Bonding and fixing to the silica film and / or the glass plate surface via the silyl group in the silica film is advantageous in improving weather resistance.
さらにまた、フッ化炭素基と炭化水素基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質が、それぞれシリル基およびシロキサン基を介して互いにまたは個々にガラス板表面に結合固定されていると、耐候性を向上する上で都合がよい。 Furthermore, a long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group, a short chain substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group, and a substance mainly composed of a siloxane group, It is convenient to improve weather resistance when they are bonded to each other or individually on the surface of the glass plate via silyl groups and siloxane groups, respectively.
また、撥水撥油防汚性被膜に含まれるフッ化炭素基と炭化水素基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質の分子組成比が、１：１０：１０〜１：０：０であると、太陽エネルギー利用装置に付着した雨滴の滑落性を制御する上で好都合である。 In addition, a long chain material mainly composed of a fluorocarbon group and a hydrocarbon group, and a short chain material mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group, contained in the water / oil repellent and antifouling film, When the molecular composition ratio of the substance having a siloxane group as a main component is 1:10:10 to 1: 0: 0, it is advantageous in controlling the sliding property of raindrops attached to the solar energy utilization device.
また、表面に撥水撥油防汚性被膜が形成されたガラス板であって、前記被膜が、少なくともフッ化炭素基と炭化水素基を主成分とする長鎖物質を含み前記被膜の臨界表面エネルギーが５〜２０ｍＮ／ｍに制御されていると、ガラス板に付着した雨滴の滑落性を制御する上で好都合である。 Further, a glass plate having a surface on which a water / oil repellent / antifouling coating is formed, wherein the coating contains a long chain substance mainly composed of at least a fluorocarbon group and a hydrocarbon group. When the energy is controlled to 5 to 20 mN / m, it is convenient for controlling the sliding property of raindrops attached to the glass plate.
また、フッ化炭素基と炭化水素基を主成分とする長鎖物質が側鎖にフッ化炭素基と炭化水素基を持つ有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質であると、被膜の耐久性を向上する上で都合がよい。 In addition, a long chain substance mainly composed of a fluorocarbon group and a hydrocarbon group is a long chain substance mainly composed of an organic fluorine-containing ether group or an organic fluorine-containing polyether group having a fluorocarbon group and a hydrocarbon group in the side chain. A chain substance is advantageous in improving the durability of the coating.
さらに、有機含フッ素エーテル基または有機含フッ素ポリエーテル基が下記式（化１または化２）に示した官能基であると、耐久性を向上できて都合がよい。
また、撥水撥油防汚性被膜がアルカリバリア膜を介して形成されていると、さらに耐候性を向上できて都合がよい。
また、複合膜がさらにメチルシリル基を含んでいると、ガラス板に付着した雨滴の滑落性を小さくできて好都合である。
Moreover, when the water / oil repellent / antifouling coating is formed via an alkali barrier film, it is advantageous in that the weather resistance can be further improved.
Further, if the composite film further contains a methylsilyl group, it is advantageous in that the sliding property of raindrops adhering to the glass plate can be reduced.
またこのとき、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)の分子混合比を、１：１０：１０〜１：０：０にしておくと、太陽エネルギー利用装置に付着した雨滴の滑落性を制御する上で好都合である。 Further, at this time, a long-chain substance (1) mainly containing a fluorocarbon group and a hydrocarbon group and containing an alkoxysilyl group, and a short-chain substance containing a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as main ingredients ( If the molecular mixing ratio of 2) and the substance (3) having an alkoxysilyl group as a main component is set to 1:10:10 to 1: 0: 0, the sliding property of raindrops attached to the solar energy utilization device is controlled. This is convenient.
さらに、少なくともフッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)として有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質を用いると、被膜の耐摩耗性を向上できて好都合である。 Further, as a long-chain substance (1) mainly comprising at least a fluorocarbon group and a hydrocarbon group and containing an alkoxysilyl group, a long-chain substance containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group and an alkoxysilyl group When used, it is advantageous in that the wear resistance of the coating can be improved.
また、有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質として下記式（化３または化４）に示した物質を用い、
フッ化炭素基と炭化水素基とアルコキシシリル基を主成分とする短鎖物質(2)としてＣＦ3−（ＣＦ2）ｏ−（ＣＨ２）２−Ｓｉ（ＯＡ）3（添え字のｏは整数、Ａはアルキル基、ＯＡはＣｌまたはＮＣＯでも良い。ただし、Ｃｌをもちいれば、製膜工程で塩酸が発生する。）を用い、アルコキシシリルキ基を主成分とする物質(3)として（ＡＯ）３Ｓｉ（ＯＳｉ（ＯＡ）２）ｐＯＡ（ｐは０または整数、Ａはアルキル基、ＯＡはＣｌまたはＮＣＯでも良い。ただし、Ｃｌをもちいれば、製膜工程で塩酸が発生する。）を用いると、雨滴転落角と耐摩耗性を同時に制御できて好都合である。 CF 3 — (CF 2 ) o — (CH 2 ) 2 —Si (OA) 3 (subscript o is a short chain substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. An integer, A may be an alkyl group, and OA may be Cl or NCO. However, if Cl is used, hydrochloric acid is generated in the film forming step), and the substance (3) having an alkoxysilyl group as a main component is used. (AO) 3 Si (OSi (OA) 2 ) p OA (p is 0 or an integer, A is an alkyl group, OA may be Cl or NCO. However, if Cl is used, hydrochloric acid is generated in the film forming step. .) Is convenient because it allows simultaneous control of the raindrop fall angle and wear resistance.
また、有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質として、下記式（化５）に示した物質を用い、
フッ化炭素基と炭化水素基とアルコキシシリル基を主成分とする短鎖物質(2)としてＣＦ3−（ＣＦ2）ｏ−（ＣＨ２）２−Ｓｉ（ＯＡ）3（添え字のｏは整数、Ａはアルキル基。）を用い、アルコキシシリルキ基を主成分とする物質(3)として（ＡＯ）３Ｓｉ（ＯＳｉ（ＯＡ）２）ｐＯＡ（Ｐは０または整数、Ａはアルキル基。）を用いても、雨滴転落角と耐摩耗性を同時に制御できて好都合である。 CF 3 — (CF 2 ) o — (CH 2 ) 2 —Si (OA) 3 (subscript o is a short chain substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. (AO) 3 Si (OSi (OA) 2 ) p OA (P is 0 or an integer, A is an alkyl group) ) Is convenient because it can control the raindrop fall angle and wear resistance at the same time.
さらにまた、シラノール縮合触媒の代わりに、ケチミン化合物、又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物、あるいはＴｉＯ２等の金属酸化物を用いると、処理時間を短縮できて都合がよい。 Furthermore, when a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, an aminoalkylalkoxysilane compound, or a metal oxide such as TiO 2 is used instead of the silanol condensation catalyst, the treatment time can be shortened. convenient.
また、シラノール縮合触媒にケチミン化合物、又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物および／あるいはＴｉＯ２等の金属酸化物を混合して用いると、さらに処理時間を短縮できて都合がよい。 In addition, when a ketimine compound, or organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxysilane compound and / or TiO 2 or other metal oxide is used in combination with the silanol condensation catalyst, the treatment time can be further shortened. Convenient.
さらに、有機溶媒としてフッ化炭素系有機溶媒や含塩素フッ化炭素系有機溶媒を用いると、前記式（化２および３）に示した物質を均一に溶解する上で都合がよい。
Furthermore, using a fluorinated carbon-based organic solvent or a chlorine-containing fluorinated carbon-based organic solvent as the organic solvent is advantageous for uniformly dissolving the substance represented by the above formulas (
また、複合膜形成前にあらかじめガラス板表面にアルカリバリア膜としてシリカ膜を形成しておくと、被膜密度と耐水性を同時に向上できて都合がよい。 また、複合膜形成後、２５０〜４５０℃で加熱すると、被膜の耐候性を向上できて好都合である。 Further, if a silica film is formed as an alkali barrier film on the surface of the glass plate in advance before forming the composite film, it is convenient because the film density and water resistance can be improved at the same time. In addition, heating at 250 to 450 ° C. after the formation of the composite film is advantageous because it can improve the weather resistance of the coating.
また、複合膜形成後、さらにメチルシリル基を含んだ物質を溶かした溶液で処理すると雨滴転落角を小さくできて都合がよい。 Further, after forming the composite film, it is convenient to treat with a solution in which a substance containing a methylsilyl group is further dissolved, so that the raindrop falling angle can be reduced.
以上説明したように、本発明の太陽エネルギー利用装置およびその製造方法では、受光面側最表面に、少なくとも有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質を含む撥水撥油防汚性被膜を形成することにより、高い耐摩耗性と雨滴滑落性と耐候性とを同時に満足させた長期亘り光利用効率が劣化しない太陽エネルギー利用装置を提供できる効果がある。 As described above, in the solar energy utilization apparatus and the manufacturing method thereof according to the present invention, the light-receiving surface-side outermost surface contains a long-chain material containing at least an organic fluorine-containing ether group or an organic fluorine-containing polyether group as a main component. By forming the water / oil repellent antifouling film, there is an effect that it is possible to provide a solar energy utilization device that does not deteriorate the light utilization efficiency over a long period of time satisfying both high wear resistance, raindrop sliding property and weather resistance.
本発明は、少なくとも受光面側最表面に、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)とシラノール縮合触媒とを有機溶媒で希釈した複合膜形成溶液を接触、反応させ撥水撥油防汚性の複合膜を形成する工程とにより、あるいは、少なくとも受光面側最表面に、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)とシラノール縮合触媒とを有機溶媒で希釈した複合膜形成溶液を接触、反応させ撥水撥油防汚性の複合膜を形成する工程と、前記ガラス板表面の余分な溶液を有機溶媒を用いて洗浄除去またはふき取り除去する工程とにより、受光面側最表面に、高耐久性の撥水撥油防汚性被膜が形成された太陽エネルギー利用装置であって、前記被膜が、フッ化炭素基と炭化水素基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質を含む複合膜であることを特徴とする太陽エネルギー利用装置を製造して提供するものである。 The present invention provides a long-chain substance (1) mainly comprising a fluorocarbon group and a hydrocarbon group and containing an alkoxysilyl group, a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group on at least the light receiving surface side outermost surface. Water- and oil-repellent and antifouling properties by contacting and reacting a short-chain substance (2) with a main component, a substance (3) with an alkoxysilyl group as a main component, and a silanol condensation catalyst diluted with an organic solvent. Or a long chain substance (1) comprising a fluorocarbon group and a hydrocarbon group as main components and an alkoxysilyl group, and a fluorocarbon group, and Contacting and reacting a composite film forming solution in which a short chain substance (2) mainly composed of hydrocarbon and alkoxysilyl groups, a substance (3) mainly composed of alkoxysilyl groups, and a silanol condensation catalyst are diluted with an organic solvent. Let water and oil repellent antifouling A highly durable water and oil repellent antifouling property is formed on the outermost surface of the light receiving surface by a step of forming a composite film and a step of cleaning or removing the excess solution on the surface of the glass plate with an organic solvent. A solar energy utilization device having a coating formed thereon, wherein the coating is composed mainly of a long-chain material mainly comprising a fluorocarbon group and a hydrocarbon group, a fluorocarbon group, a hydrocarbon group, and a silyl group. The present invention is to manufacture and provide a solar energy utilization device, which is a composite film including a short chain material and a material mainly composed of a siloxane group.
以下、本発明の撥水撥油防汚性に優れた太陽エネルギー利用装置の一例としてとして、太陽電池パネルを取り上げ、詳細に説明する。
なお、以下の実施例においては、とくに記載していない限り分子組成比はモル比を意味する。また、特に記載のない％は重量％を意味する。なお、本願発明はこれら実施例によって何ら限定されるものではない。
Hereinafter, a solar cell panel will be taken up and described in detail as an example of a solar energy utilization device excellent in water and oil repellency and antifouling properties of the present invention.
In the following examples, the molecular composition ratio means a molar ratio unless otherwise specified. Further, “%” not specifically mentioned means “% by weight”. In addition, this invention is not limited at all by these Examples.
まず、あらかじめ図１に示したような太陽電池の光入射側透明基材となるガラス板１を用意し、裏面に印刷法を用いてITO透明電極２、銀ペースト櫛形電極３、ｎ型アモルファスSi層４とｐ型アモルファスSi層５を順に形成し、さらにその上に反射膜を兼ねたアルミニウムのバック電極６を蒸着形成して太陽電池セルを形成した。
一方、少なくともフッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)として、下記式（化６）に示した側鎖にフッ化炭素基と炭化水素基を持つ有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質を用い、
First, a
On the other hand, as a long-chain substance (1) having at least a fluorocarbon group and a hydrocarbon group as main components and containing an alkoxysilyl group, a side chain represented by the following formula (Chemical Formula 6) has a fluorocarbon group and a hydrocarbon group. Using a long-chain substance containing an organic fluorine-containing ether group or organic fluorine-containing polyether group and alkoxysilyl group,
フッ化炭素基と炭化水素基とアルコキシシリル基を主成分とする短鎖物質(2)としてＣＦ3−（ＣＦ2）７−（ＣＨ２）２−Ｓｉ（ＯＣＨ3）3を用い、アルコキシシリルキ基を主成分とする物質(3)としてＳｉ（ＯＣＨ3）４を用い、シラノール縮合触媒としてジブチル錫オキサイドを用い、それぞれ０．０１、０．０１、０．００３、０．００００５Ｍ／Ｌとなるようにジクロロペンタフルオロプロパン３０％含有ペンタフルオロブタン溶媒（含塩素フッ化炭素系有機溶媒）に溶解して複合膜形成溶液を作成した。 CF 3 — (CF 2 ) 7 — (CH 2 ) 2 —Si (OCH 3 ) 3 is used as the short chain substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group, and alkoxysilyl is used. Si (OCH 3 ) 4 is used as the substance (3) mainly containing a key group, dibutyltin oxide is used as the silanol condensation catalyst, and 0.01, 0.01, 0.003, and 0.00005 M / L, respectively. Thus, a composite film forming solution was prepared by dissolving in a pentafluorobutane solvent (chlorine-containing fluorocarbon organic solvent) containing 30% dichloropentafluoropropane.
次に、この複合膜形成溶液を、普通の空気中で（相対湿度５３％、別の実験では６５％でも問題なかった。）で良く洗浄した前記ガラス板１の電池セル反対面（光７入射面側）に塗布して１時間反応させた。その後、すぐに表面の余分な複合膜形成溶液をクロロホルムで洗浄除去すると、図１に示したような有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質８とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質９とシロキサン基を主成分とする物質１０の組成比が略１：１：０．３であり、フッ化炭素基間にシロキサン記が網目状に入った膜厚が略３ｎｍ程度の複合膜１１を前記ガラス板１の電池セル１２の反対面に形成でき、防汚離水性に優れた太陽電池パネル１３を製造できた。
Next, this composite film-forming solution was washed well in normal air (relative humidity 53%, 65% in another experiment). And coated for 1 hour. Immediately thereafter, the excess composite film forming solution on the surface is washed away with chloroform. As shown in FIG. 1, the long-
なお、ここで、ガラス板１の表面には、吸着水や水酸基が多数含まれているので、前記有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)の≡Ｓｉ（ＯＣＨ３）基は、前記ガラス板表面の水酸基や吸着水がシラノール縮合触媒の存在下で脱アルコール（この場合は、脱ＣＨ３ＯＨ）反応して、ガラス板表面全面に亘り互いにあるいは表面と化学結合した有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質を含む複合膜が前記ガラス板表面に形成された。
Here, since the surface of the
このときの複合膜の膜厚は、ナノメートル程度であったので、ガラス板の透明性を損なうことは全くなかった。また、ガラス板表面の水滴接触角は、洗浄工程の有無に関わらず、略１１３度（臨界表面エネルギーは７ｍＮ／ｍ程度）であり、テフロン（登録商標）コート以上の撥水撥油防汚性を付与できた。また、５０μＬの水滴を滴下した場合の転落角度は１２度であった。 Since the film thickness of the composite film at this time was about nanometer, the transparency of the glass plate was not impaired at all. In addition, the water droplet contact angle on the glass plate surface is approximately 113 degrees (critical surface energy is about 7 mN / m) regardless of the presence or absence of the cleaning process, and the water and oil repellency and antifouling properties are higher than those of Teflon (registered trademark) coats. Could be granted. Moreover, the fall angle | corner at the time of dripping a 50 microliter water drop was 12 degree | times.
この複合膜は、ガラス板表面とシロキサン結合を介して共有結合しているため、図２に示したように、摩耗試験では、加重６００ｇ／ｃｍ２の条件下で往復６０００回のこすり後でも、水滴接触角は、１１０度以上を維持できた。この条件は、布地で表面を数十万回拭う条件に相当する。 Since this composite film is covalently bonded to the glass plate surface via a siloxane bond, as shown in FIG. 2, in the abrasion test, even after rubbing 6000 times under a load of 600 g / cm 2 , The water droplet contact angle could be maintained at 110 degrees or more. This condition corresponds to the condition of wiping the surface hundreds of thousands of times with fabric.
この複合膜に於いて、耐摩耗性が大幅に向上した理由は、有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質が複合膜に表面に突出しするためと考えられた。したがって、この条件を満たすためには、フッ化炭素基と炭化水素基を主成分とする長鎖物質の分子長がフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質の分子長の２倍以上が望ましいと結論された。
なお、本プロセスでは、被膜形成材料としてアルコキシシラン系の薬剤のみを用いているため塩酸が発生することはなかった。
The reason why the wear resistance of the composite film is greatly improved is considered to be that long-chain substances mainly composed of organic fluorine-containing ether groups or organic fluorine-containing polyether groups protrude from the surface of the composite film. It was. Therefore, in order to satisfy this condition, the molecular length of a long-chain substance mainly composed of a fluorocarbon group and a hydrocarbon group is shorter than that of a short-chain substance mainly composed of a fluorocarbon group, a hydrocarbon group and a silyl group. It was concluded that more than twice the molecular length is desirable.
In this process, hydrochloric acid was not generated because only the alkoxysilane-based chemical was used as the film forming material.
（比較例１）
参考として、実施例１に於いて、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)である有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質を含めず、フッ化炭素基と炭化水素基とアルコキシシリル基を主成分とする短鎖物質(2)がＣＦ3−（ＣＦ2）７−（ＣＨ２）２−Ｓｉ（ＯＣＨ３）３であり、アルコキシシリルキ基を主成分とする物質(3)がＳｉ（ＯＣＨ３）４であり、フッ化炭素基と炭化水素基とアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリルキ基を主成分とする物質(3)の濃度をそれぞれ０．０１と０．００３Ｍ／Ｌとし、他の条件は実施例１と全て同条件で試作した場合、初期水滴接触角は１０９度となった。また、耐摩耗試験における水滴接触角変化の結果を比較例１として図２に示す。
(Comparative Example 1)
As a reference, in Example 1, an organic fluorine-containing ether group or organic fluorine-containing polyether group and alkoxy which are long-chain substances (1) mainly composed of a fluorocarbon group and a hydrocarbon group and containing an alkoxysilyl group A short chain substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group is excluded from a long chain substance containing a silyl group. CF 3 — (CF 2 ) 7 — (CH 2 ) 2 — The substance (3) which is Si (OCH 3 ) 3 and has an alkoxysilyl group as a main component is Si (OCH 3 ) 4 and is a short component which mainly has a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group. In the case where the concentration of the chain substance (2) and the substance (3) mainly composed of alkoxysilyl groups is 0.01 and 0.003 M / L, respectively, and other conditions are made under the same conditions as in Example 1, The initial water droplet contact angle was 109 degrees. Moreover, the result of the water droplet contact angle change in the abrasion resistance test is shown in FIG.
（比較例２）
さらに、実施例１に於いて、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)である有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質とアルコキシシリルキ基を主成分とする物質(3)を含めず、フッ化炭素基と炭化水素基とアルコキシシリル基を主成分とする短鎖物質(2)がＣＦ3−（ＣＦ2）７−（ＣＨ２）２−Ｓｉ（ＯＣＨ３）３であり、他の条件は実施例１と全て同条件で試作した場合、初期水滴接触角は１１２度となった。また、被膜の耐摩耗試験における水滴接触角変化の結果を比較例２として図２に示す。
(Comparative Example 2)
Further, in Example 1, the organic fluorine-containing ether group or the organic fluorine-containing polyether group and the alkoxysilyl which are long-chain substances (1) mainly comprising a fluorocarbon group and a hydrocarbon group and containing an alkoxysilyl group The long chain substance containing a group and the substance (3) containing an alkoxysilyl group as a main component are not included, but the short chain substance (2) containing a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group as a main component is CF 3 - (CF 2) 7 - ( CH 2) 2 -Si (OCH 3) 3, and other conditions when the prototype in all same condition as in example 1, the initial contact angle of water droplet became 112 degrees. In addition, the result of the water droplet contact angle change in the abrasion resistance test of the coating is shown in FIG.
図２より明らかなように、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)である有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質を除けば、初期値の水滴接触角は実用レベルであるが、耐摩耗性がかなり劣化することが判る。 As is clear from FIG. 2, the organic fluorine-containing ether group or the organic fluorine-containing polyether group and the alkoxysilyl group, which are long-chain substances (1) mainly composed of a fluorocarbon group and a hydrocarbon group and containing an alkoxysilyl group. Except for long-chain materials containing, the initial water droplet contact angle is at a practical level, but it can be seen that the wear resistance is considerably deteriorated.
また、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)である有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質とアルコキシシリルキ基を主成分とする物質(3)の両方を除いても、初期値の水滴接触角は実用レベルであるが、耐摩耗性が大幅に劣化することが判る。 Further, a long-chain substance containing an organic fluorine-containing ether group or an organic fluorine-containing polyether group and an alkoxysilyl group, which is a long-chain substance (1) mainly composed of a fluorocarbon group and a hydrocarbon group, and containing an alkoxysilyl group; Even when both of the substances (3) containing the alkoxysilyl group as a main component are removed, the initial water droplet contact angle is at a practical level, but it can be seen that the wear resistance is greatly deteriorated.
一方、反応後、表面の余分な複合膜形成溶液をエタノールを含むウエスでふき取った場合には、膜厚が略１５ｎｍとなり、初期水滴接触角が略１１０度（臨界表面エネルギーは８ｍＮ／ｍ程度）の複合膜を形成できた。また、このときの、耐摩耗性は、洗浄した場合と大きな違いはなかった。 On the other hand, after the reaction, when the excess composite film forming solution on the surface is wiped off with a waste cloth containing ethanol, the film thickness is about 15 nm and the initial water droplet contact angle is about 110 degrees (the critical surface energy is about 8 mN / m). A composite membrane of In addition, the wear resistance at this time was not significantly different from the case of cleaning.
なお、本実施例では、複合膜形成溶液を塗布する方法を用いたが、塗布方法には、刷毛塗り、ロールコート、スプレイ塗布、何れの方法でも問題はなく、複合膜形成溶液に浸漬しても、実質的にガラスと複合膜形成溶液が一定時間接触していれば同様の性能の被膜が得られた。
また、メトキシ基の代わりにエトキシ基、あるいは反応は異なるがＣｌやＮＣＯ基でもほぼ同様に製膜できた。ただし、Ｃｌをもちいれば、製膜工程で塩酸が発生する。
In this example, the method of applying the composite film forming solution was used. However, there is no problem in any of the coating method, brush coating, roll coating, spray coating, and soaking in the composite film forming solution. In addition, when the glass and the composite film forming solution were substantially in contact with each other for a certain time, a film having the same performance was obtained.
Further, an ethoxy group instead of a methoxy group, or a Cl or NCO group, although the reaction was different, could be formed almost similarly. However, if Cl is used, hydrochloric acid is generated in the film forming process.
それぞれの濃度を０．０１、０．０１、０．０１、０．００００５Ｍ／Ｌとし、その他の条件を同じとして作成した場合には、組成比が略１：１：１であり、膜厚が略５ｎｍ程度で、初期水滴接触角が略１０２度（臨界表面エネルギーは２０ｍＮ／ｍ程度）の耐摩耗性に優れた複合膜を形成できた。 When the respective concentrations were 0.01, 0.01, 0.01, 0.00005 M / L and other conditions were the same, the composition ratio was approximately 1: 1: 1, and the film thickness was A composite film excellent in abrasion resistance having an initial water droplet contact angle of about 102 degrees (critical surface energy of about 20 mN / m) was formed at about 5 nm.
ここで、撥水撥油防汚性複合膜を形成したガラス板の表面エネルギーは、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)である有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)の組成にほぼ依存するので、１：１０：１０乃至１：０：０の範囲で仕込み組成を変えれば、表面エネルギーを２０〜５ｍＮ／ｍ程度に制御でき、水滴接触角を調節できた。さらに、１：１０：１０乃至１：０．１：０．１の範囲で仕込み組成を変えれば、水滴接触角を制御しながら耐摩耗性を同時に確保できた。 Here, the surface energy of the glass plate on which the water / oil / oil repellent / anti-fouling composite film is formed contains an organic substance which is a long-chain substance (1) mainly composed of a fluorocarbon group and a hydrocarbon group and containing an alkoxysilyl group. Long-chain substances containing fluorine ether groups or organic fluorine-containing polyether groups and alkoxysilyl groups; short-chain substances mainly containing fluorocarbon groups, hydrocarbon groups and alkoxysilyl groups (2); and alkoxysilyl groups as main ingredients The surface energy can be controlled to about 20 to 5 mN / m by changing the charged composition in the range of 1:10:10 to 1: 0: 0, and the water droplet contact angle can be controlled. Could be adjusted. Furthermore, if the preparation composition was changed in the range of 1:10:10 to 1: 0.1: 0.1, the wear resistance could be secured at the same time while controlling the water droplet contact angle.
さらに、あらかじめガラス基板から溶出してくるアルカリを防止する目的で０：０：１の組成で形成したアルカリバリア膜（以後、シリカ膜１４という。）を介して複合形を形成した（図３）場合、シリカ膜がない場合に比べて複合膜のフッ化炭素基の密度を向上でき、耐水性が向上してさらに２〜３倍耐久性が向上した。 Further, a composite form was formed through an alkali barrier film (hereinafter referred to as silica film 14) formed with a composition of 0: 0: 1 in order to prevent alkali eluted from the glass substrate in advance (FIG. 3). In this case, the density of the fluorocarbon group of the composite film can be improved as compared with the case where there is no silica film, the water resistance is improved, and the durability is further improved 2 to 3 times.
またここで、複合膜形成後、２５０〜４５０℃で３０分程度加熱するとさらに耐候性を向上できた。なお、加熱温度が２５０〜３００℃であれば、通常の空気中で加熱しても問題なかったが、３２０〜４５０℃であれば、被膜の酸化を防ぐため実質的に酸素を含まない雰囲気中で行う必要があった。 Here, after the composite film was formed, the weather resistance could be further improved by heating at 250 to 450 ° C. for about 30 minutes. If the heating temperature was 250 to 300 ° C., there was no problem even if heating was performed in normal air, but if it was 320 to 450 ° C., in an atmosphere substantially free of oxygen in order to prevent oxidation of the film. It was necessary to do in.
また、複合膜形成後、前記加熱前にさらにメチルシリル基を含んだ物質として、例えばトリメチルメトキシシラン（（Ｈ３Ｃ）３ＳｉＯＣＨ３）を用い、シラノール縮合触媒としてジブチル錫オキサイドを用い、それぞれ０．００３、０．００００５Ｍ／Ｌとなるようにノナンに溶解した溶液で同様の処理を行うと、複合膜中には一部水酸基１５が含まれているので、この水酸基とトリメチルメトキシシランが脱アルコール反応して、図４に示した様に、メチルシリル基１６を含んだ撥水撥油防汚性被膜１１を形成できた。なお、この様に作成された被膜では、メチルシリル基を含んだ処理液で処理する前の複合膜に比べて５０μＬの水滴で転落角度を８〜３度低減できた。
Further, after the formation of the composite film, before the heating, for example, trimethylmethoxysilane ((H 3 C) 3 SiOCH 3 ) is used as a substance further containing a methylsilyl group, and dibutyltin oxide is used as a silanol condensation catalyst. When the same treatment is performed with a solution dissolved in nonane so as to be 003 and 0.00005 M / L, the hydroxyl group and trimethylmethoxysilane are subjected to a dealcoholization reaction because the hydroxyl group 15 is partially contained in the composite film. Then, as shown in FIG. 4, a water / oil repellent antifouling film 11 containing
実施例１に於いて、反応後洗浄せずに前記非水系有機溶媒を蒸発させる（この場合、６０乃至１００℃で太陽電池セルが形成されたガラス板を加熱すると、溶媒の蒸発を早めることが可能であり、蒸発時間を短縮できた。）と、有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質の組成比が略１：１：０．３であり、膜厚が略３０ｎｍのポリマー状の複合膜が前記ガラス板表面に形成できた。 In Example 1, the non-aqueous organic solvent is evaporated without washing after the reaction (in this case, heating the glass plate on which the solar cells are formed at 60 to 100 ° C. can accelerate the evaporation of the solvent. And the evaporation time can be shortened.), A long chain substance mainly composed of an organic fluorine-containing ether group or an organic fluorine-containing polyether group, a fluorocarbon group, a hydrocarbon group, and a silyl group. The composition ratio of the short chain substance and the substance mainly composed of a siloxane group was about 1: 1: 0.3, and a polymer composite film having a film thickness of about 30 nm could be formed on the surface of the glass plate.
なお、ここで、ガラス板表面には吸着水やナチュラルオキサイドの水酸基が多数含まれているので、塗布された複合膜形成用溶液は、前記フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)である有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)の≡Ｓｉ（ＯＣＨ３）基は、前記ガラス板表面の水酸基や吸着水がシラノール縮合触媒の存在下で脱アルコール（この場合は、脱ＣＨ３ＯＨ）反応して、ガラス板表面全面に亘り互いにあるいは表面と化学結合した有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質を含む複合膜が前記ガラス板表面に形成した。 Here, since the surface of the glass plate contains a large number of adsorbed water and natural oxide hydroxyl groups, the applied solution for forming a composite film is composed mainly of the fluorocarbon group and hydrocarbon group, and alkoxy. The main chain is a long chain substance containing an organic fluorine-containing ether group or organic fluorine-containing polyether group and an alkoxysilyl group, and a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group. The ≡Si (OCH 3 ) group of the short-chain material (2) and the material (3) containing an alkoxysilyl group as a main component is de-alcoholized in the presence of a silanol condensation catalyst when hydroxyl groups and adsorbed water on the glass plate surface are present. In this case, an organic fluorine-containing ether group or an organic fluorine-containing polyether group chemically bonded to each other or the surface over the entire surface of the glass plate is mainly reacted by de-CH 3 OH) reaction. A composite film containing a long chain substance as a component, a short chain substance mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group and a substance mainly composed of a siloxane group was formed on the glass plate surface.
さらに、空気中で溶媒を蒸発させると、ガラス板表面に残った有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質(1)とフッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)は、空気中の水分と互いに加水分解して、前記ガラス板表面に形成された有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質を含む複合膜と一体化して、有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質とシロキサン基を主成分とする物質を含むポリマー状の複合膜が前記ガラス板表面に形成した。 Further, when the solvent is evaporated in the air, the long-chain substance (1) containing the organic fluorine-containing ether group or the organic fluorine-containing polyether group and the alkoxysilyl group remaining on the glass plate surface, the fluorocarbon group and the hydrocarbon group And the short-chain substance (2) mainly composed of alkoxysilyl groups and the substance (3) mainly composed of alkoxysilyl groups are hydrolyzed with water in the air and formed on the surface of the glass plate. Includes long-chain substances mainly composed of fluorine-containing ether groups or organic fluorine-containing polyether groups, short-chain substances mainly composed of fluorocarbon groups, hydrocarbon groups and silyl groups, and substances mainly composed of siloxane groups. Integrated with the composite membrane, long-chain materials mainly composed of organic fluorine-containing ether groups or organic fluorine-containing polyether groups, short-chain materials mainly composed of fluorocarbon groups, hydrocarbon groups, and silyl groups, and silos Polymeric composite film comprising a material whose main component an acid group was formed on the glass plate surface.
このとき得られる複合膜の膜厚は、数十ナノメートルレベルとなるが、ガラス板の透明性を損なうレベルではなかった。また、ガラス板表面の水滴接触角は、洗浄工程の有無に関わらず、略１０８度（臨界表面エネルギーは１５ｍＮ／ｍ程度）であり、テフロン（登録商標）コート以上の撥水撥油防汚性を付与できた。
また、摩耗試験結果は、実施例１に比べてさらに１０倍程度改善されていた。
Although the film thickness of the composite film obtained at this time is on the order of several tens of nanometers, it was not at a level that impairs the transparency of the glass plate. In addition, the water droplet contact angle on the glass plate surface is approximately 108 degrees (critical surface energy is about 15 mN / m) regardless of the presence or absence of the cleaning process, and the water and oil repellency and antifouling property is higher than that of Teflon (registered trademark) coat. Could be granted.
Moreover, the abrasion test result was further improved about 10 times compared with Example 1.
実施例１において、フッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)を除いて同様の方法で被膜を製造した。
この場合、当然有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質とシロキサン基を主成分とする物質を含む膜厚が略５ｎｍの複合膜が前記ガラス板表面に形成できた。
In Example 1, a coating film was produced in the same manner except for the short chain substance (2) mainly composed of a fluorocarbon group, a hydrocarbon group and an alkoxysilyl group.
In this case, naturally, a composite film having a film thickness of about 5 nm is formed on the surface of the glass plate, including a long-chain substance mainly composed of an organic fluorine-containing ether group or an organic fluorine-containing polyether group and a substance mainly composed of a siloxane group. did it.
このとき、複合膜の膜厚は、やはりナノメートル程度であったので、ガラス板の透明性を損なうことは全くなかった。また、ガラス板表面の水滴接触角は、洗浄工程の有無に関わらず、略１１０度（臨界表面エネルギーは１０ｍＮ／ｍ程度）であり、テフロン（登録商標）コート以上の撥水撥油防汚性を付与できた。
また、摩耗試験では、実施例１とほぼ同様の結果を得た。
At this time, since the film thickness of the composite film was about nanometer, the transparency of the glass plate was not impaired at all. In addition, the water droplet contact angle on the glass plate surface is approximately 110 degrees (critical surface energy is about 10 mN / m) regardless of the presence or absence of the cleaning process, and the water and oil repellency and antifouling property of Teflon (registered trademark) or higher. Could be granted.
Further, in the wear test, almost the same result as in Example 1 was obtained.
実施例１において、アルコキシシリル基を主成分とする物質(3)を除いて同様の方法で被膜を製造した。
この場合、当然有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質とフッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質を含む膜厚が略４ｎｍの複合膜が前記ガラス板表面に形成できた。
In Example 1, a film was produced in the same manner except for the substance (3) mainly composed of alkoxysilyl groups.
In this case, of course, the film thickness including a long chain material mainly composed of an organic fluorine-containing ether group or an organic fluorine-containing polyether group and a short chain material mainly composed of a fluorocarbon group, a hydrocarbon group, and a silyl group is substantially reduced. A 4 nm composite film could be formed on the glass plate surface.
このとき、複合膜の膜厚は、やはりナノメートル程度であったので、ガラス板の透明性を損なうことは全くなかった。また、ガラス板表面の水滴接触角は、洗浄工程の有無に関わらず、略１１４度（臨界表面エネルギーは６ｍＮ／ｍ程度）であり、テフロン（登録商標）コーに比べると格段に優れた撥水撥油防汚性を付与できた。
また、摩耗試験では、実施例１と比べると多少劣化が早かったが、ほぼ同様の結果を得た。
At this time, since the film thickness of the composite film was about nanometer, the transparency of the glass plate was not impaired at all. In addition, the water droplet contact angle on the glass plate surface is approximately 114 degrees (critical surface energy is about 6 mN / m) regardless of the presence or absence of the cleaning process, and water repellent that is much superior to Teflon (registered trademark) Co. Oil repellency and antifouling properties were imparted
In the abrasion test, the deterioration was somewhat faster than that in Example 1, but almost the same result was obtained.
実施例１において、フッ化炭素基および炭化水素基およびアルコキシシリル基を主成分とする短鎖物質(2)とアルコキシシリル基を主成分とする物質(3)を除いて同様の方法で被膜を製造した。
この場合、当然有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖長鎖物質(1)で膜厚が略３ｎｍの被膜が前記ガラス板表面に形成できた。
In Example 1, the coating film was formed in the same manner except for the short chain substance (2) mainly composed of fluorocarbon group, hydrocarbon group and alkoxysilyl group and the substance (3) mainly composed of alkoxysilyl group. Manufactured.
In this case, naturally, a coating having a film thickness of about 3 nm was formed on the surface of the glass plate with the long-chain long-chain substance (1) mainly composed of the organic fluorine-containing ether group or the organic fluorine-containing polyether group.
このとき、複合膜の膜厚は、やはりナノメートル程度であったので、ガラス板の透明性を損なうことは全くなかった。また、ガラス板表面の水滴接触角は、洗浄工程の有無に関わらず、略１１６度（臨界表面エネルギーは５ｍＮ／ｍ程度）であり、テフロン（登録商標）コーに比べると格段に優れた撥水撥油防汚性を付与できた。 At this time, since the film thickness of the composite film was about nanometer, the transparency of the glass plate was not impaired at all. In addition, the water droplet contact angle on the glass plate surface is approximately 116 degrees (critical surface energy is about 5 mN / m) regardless of whether or not a cleaning process is performed, and water repellent that is remarkably superior to Teflon (registered trademark) Co. Oil repellency and antifouling properties could be imparted.
摩耗試験では、実施例１と比べて多少劣化が早かったが、実用レベルで使用できる被膜であった。 In the abrasion test, although the deterioration was somewhat faster than that in Example 1, it was a coating that could be used at a practical level.
さらに、実施例１において、上述のシラノール縮合触媒の代わりに、ケチミン化合物、又は、ＴｉＯ２等の金属酸化物、有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物が利用できた。 Furthermore, in Example 1, a ketimine compound or a metal oxide such as TiO 2 , an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound could be used in place of the above silanol condensation catalyst. .
例えば、実施例１に置いて前述のシラノール縮合触媒の代わりに、ケチミン化合物（ジャパンエポキシレジン社のＨ３、およびチッソ社のサイラエースＳ３４０を用いてみたが、性能はほぼ同じであった。）を同じ濃度で用いた場合、反応時間を３０分まで短縮できた。 For example, in place of the silanol condensation catalyst described in Example 1, the ketimine compound (H3 from Japan Epoxy Resin and Silaace S340 from Chisso was used, but the performance was almost the same). When used in concentration, the reaction time could be shortened to 30 minutes.
さらに、実施例１において、前述のシラノール縮合触媒とケチミン化合物、又は、ＴｉＯ２等の金属酸化物、有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物を１：９〜９：１で混合して用いると、さらにさらに反応時間を短縮できた。
具体的には、実施例１に置いて上述のシラノール縮合触媒濃度を半分にして、上述のケチミン化合物（例えば、Ｓ３４０）を等モル混合した場合（１：１）、反応時間を２０分まで短縮できた。
Furthermore, in Example 1, the above-mentioned silanol condensation catalyst and ketimine compound, or metal oxide such as TiO 2 , organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxysilane compound are used at 1: 9 to 9: When mixed with 1 and used, the reaction time could be further shortened.
Specifically, when the above-mentioned silanol condensation catalyst concentration is halved in Example 1 and the above-mentioned ketimine compound (eg, S340) is equimolarly mixed (1: 1), the reaction time is shortened to 20 minutes. did it.
以上に述べた全ての実施例に於いて、シラノール縮合触媒として、カルボン酸金属塩、カルボン酸エステル金属塩、カルボン酸金属塩ポリマー、カルボン酸金属塩キレート、チタン酸エステル及びチタン酸エステルキレート類が利用可能である。さらに具体的には、酢酸第１錫、ジブチル錫ジラウレート、ジブチル錫ジオクテート、ジブチル錫ジアセテート、ジオクチル錫ジラウレート、ジオクチル錫ジオクテート、ジオクチル錫ジアセテート、ジオクタン酸第１錫、ナフテン酸鉛、ナフテン酸コバルト、２−エチルヘキセン酸鉄、ジオクチル錫ビスオクチリチオグリコール酸エステル塩、ジオクチル錫マレイン酸エステル塩、ジブチル錫マレイン酸塩ポリマー、ジメチル錫メルカプトプロピオン酸塩ポリマー、ジブチル錫ビスアセチルアセテート、ジオクチル錫ビスアセチルラウレート、テトラブチルチタネート、テトラノニルチタネート、及びビス（アセチルアセトニル）ジープロピルチタネートを用いることが可能である。 In all the examples described above, as the silanol condensation catalyst, a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal salt polymer, a carboxylic acid metal salt chelate, a titanate ester, and a titanate ester chelate are used. Is available. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyl Laurate, tetrabutyl titanate, tetranonyl titanate, and bis (acetylacetonyl) dipropyl titanate can be used.
また、利用できるケチミン化合物は特に限定されるものではないが、例えば、２，５，８−トリアザ−１，８−ノナジエン、３，１１−ジメチル−４，７，１０−トリアザ−３，１０−トリデカジエン、２，１０−ジメチル−３，６，９−トリアザ−２，９−ウンデカジエン、２，４，１２，１４−テトラメチル−５，８，１１−トリアザ−４，１１−ペンタデカジエン、２，４，１５，１７−テトラメチル−５，８，１１，１４−テトラアザ−４，１４−オクタデカジエン、２，４，２０，２２−テトラメチル−５，１２，１９−トリアザ−４，１９−トリエイコサジエン等がある。 Further, the ketimine compound that can be used is not particularly limited. For example, 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza-3,10- Tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadiene, 2, , 4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza-4,19 -There is trieicosadiene.
また、利用できる有機酸としても特に限定されるものではないが、例えば、ギ酸、あるいは酢酸、プロピオン酸、ラク酸、マロン酸等があり、ほぼ同様の効果があった。 Further, the organic acid that can be used is not particularly limited, but there are, for example, formic acid, acetic acid, propionic acid, lactic acid, malonic acid, and the like, which have almost the same effects.
なお、複合膜形成溶液の溶媒を蒸発させて被膜を形成する場合には、複合膜形成溶液に用いる非水系の溶媒の沸点は、低いほど早く蒸発除去できるので都合がよいが、取扱いの上では５０〜１５０℃程度がよかった。 When forming a film by evaporating the solvent of the composite film forming solution, the lower the boiling point of the non-aqueous solvent used in the composite film forming solution is, the more convenient it is because it can be removed by evaporation earlier. About 50-150 degreeC was good.
一方、後洗浄を行う場合には、複合膜形成溶液に用いるフッ化炭素系有機溶媒の沸点は、高いほど安定しているが、取扱いの上では１５０〜３５０℃程度がよかった。 On the other hand, when post-cleaning is performed, the higher the boiling point of the fluorocarbon organic solvent used in the composite film forming solution is, the more stable it is.
なお、前記フッ化炭素系有機溶媒には、フロン系溶媒や、フロリナート（３Ｍ社製品）、アフルード（旭ガラス社製品）等があるが、これらは１種単独で用いても良いし、良く混ざるものなら２種以上を組み合わせてもよい。さらに、含塩素フッ化炭素系有機溶媒そのまま、あるいはクロロホルム等有機塩素系の溶媒を添加しても良かった。さらにまた、吸着溶媒として、水とアルコール（水とアルコールの組成比は、体積比で２：１〜１０：１で、アルコールの種類は、エタノールが良かったが、プロパノールやブタノール、エチレングリコールでも使用可能であった。）の混合溶媒を用いる場合には、シラノール縮合触媒や助触媒であるケチミン等は使用できないが、触媒無しでも超音波分散しておけば１時間程度で良好な化学吸着単分子膜を形成できた。 In addition, although the fluorocarbon organic solvent includes a chlorofluorocarbon solvent, Fluorinert (product of 3M), Afludo (product of Asahi Glass), these may be used alone or mixed well. If it is a thing, you may combine 2 or more types. Further, it is also possible to add a chlorine-containing fluorinated carbon-based organic solvent as it is or an organic chlorine-based solvent such as chloroform. Furthermore, as an adsorbing solvent, water and alcohol (the composition ratio of water and alcohol is 2: 1 to 10: 1 by volume, and the type of alcohol is ethanol, but propanol, butanol, and ethylene glycol are also used. In the case of using a mixed solvent of 1), a silanol condensation catalyst or a co-catalyst such as ketimine cannot be used. A film could be formed.
さらに、洗浄用の有機溶媒としては、水を含まない炭化水素系溶媒、あるいはフッ化炭素系溶媒やシリコーン系溶媒を用いることが可能であるが、特に沸点が５０〜３００℃のものが使用に適していた。 Furthermore, as the organic solvent for washing, it is possible to use a hydrocarbon solvent that does not contain water, or a fluorocarbon solvent or a silicone solvent, and those having a boiling point of 50 to 300 ° C. are particularly suitable for use. It was suitable.
具体的に使用可能なものは、石油ナフサ、ソルベントナフサ、石油エーテル、石油ベンジン、イソパラフィン、ノルマルパラフィン、デカリン、工業ガソリン、灯油、ジメチルシリコーン、フェニルシリコーン、アルキル変性シリコーン、ポリエーテルシリコーン等を挙げることができる。 Specific examples include petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, dimethyl silicone, phenyl silicone, alkyl-modified silicone, polyether silicone, etc. Can do.
さらにまた、フッ化炭素基と炭化水素基を主成分とし且つアルコキシシリル基を含む長鎖物質(1)である有機含フッ素エーテル基または有機含フッ素ポリエーテル基およびアルコキシシリル基を含む長鎖物質には、下記式（化３または化４）が利用できた。また、耐光性は多少悪くなるが、下記式（化５）で示される物質が利用できたが、何れも平均分子量は１０００〜５０００程度のものが利用しやすかった。
Furthermore, a long-chain material containing an organic fluorine-containing ether group or organic fluorine-containing polyether group and an alkoxysilyl group, which is a long-chain material (1) mainly composed of a fluorocarbon group and a hydrocarbon group and containing an alkoxysilyl group The following formula (
さらに具体的には、下記式（化７）や式（化８）で示される物質が利用できた。 More specifically, substances represented by the following formula (Chemical Formula 7) and Formula (Chemical Formula 8) can be used.
さらにまた、アルコキシシリル基を主成分とする物質(3)として（ＡＯ）３Ｓｉ（ＯＳｉ（ＯＡ）２）ｐＯＡ（Ｐは０〜１０、Ａは、メチル基やチル基のアルキル基、ＯＡはＣｌまたはＮＣＯでも良い。ただし、Ｃｌをもちいれば、製膜工程で塩酸が発生する。）が挙げられるが、以下に示す物質(１)-(１４)が使用しやすかった。 Furthermore, (AO) 3 Si (OSi (OA) 2 ) p OA (P is 0 to 10, A is a methyl group or til alkyl group, OA as the substance (3) having an alkoxysilyl group as a main component May be Cl or NCO (however, if Cl is used, hydrochloric acid is generated in the film forming step), the following substances (1) to (14) are easy to use.
（１）Ｓｉ（ＯＣＨ３）４
（２）ＳｉＨ（ＯＣＨ３）3
（３）ＳｉＨ2（ＯＣＨ３）2
（４）（ＣＨ３Ｏ）3Ｓｉ（ＯＳｉ（ＯＣＨ３）2）ｍＯＣＨ３
（５）Ｓｉ（ＯＣ２Ｈ５）3
（６）ＳｉＨ（ＯＣ２Ｈ５）3
（７）ＳｉＨ2（ＯＣ２Ｈ５）2
（８）（Ｈ５Ｃ２Ｏ）3Ｓｉ（ＯＳｉ（ＯＣ２Ｈ５）2）ｍＯＣ２Ｈ５
ここで、ｍは、１〜６整数を表す。
(1) Si (OCH 3 ) 4
(2) SiH (OCH 3 ) 3
(3) SiH 2 (OCH 3 ) 2
(4) (CH 3 O) 3 Si (OSi (OCH 3 ) 2 ) m OCH 3
(5) Si (OC 2 H 5 ) 3
(6) SiH (OC 2 H 5 ) 3
(7) SiH 2 (OC 2 H 5 ) 2
(8) (H 5 C 2 O) 3 Si (OSi (OC 2 H 5 ) 2 ) m OC 2 H 5
Here, m represents an integer of 1 to 6.
なお、本願発明は、太陽エネルギー利用装置であればどのような物にでも適用可能である。具体的には、太陽電池パネルの他、太陽熱温水器や温室等がある。 The present invention can be applied to any solar energy utilization device. Specifically, there are a solar water heater, a greenhouse, etc. in addition to a solar battery panel.
１ ガラス板
２ ITO透明電極
３ 銀ペースト櫛形電極
４ ｎ型アモルファスSi半導体層
５ ｐ型アモルファスSi半導体層
６ Ａｌ蒸着バック電極
７ 光
８ 有機含フッ素エーテル基または有機含フッ素ポリエーテル基を主成分とする長鎖物質
９ フッ化炭素基と炭化水素基とシリル基を主成分とする短鎖物質
１０ シロキサン基を主成分とする物質
１１ 撥水撥油防汚性の複合膜
１２ 太陽電池セル
１３ 光入射面側に撥水撥油防汚性被膜が形成された太陽電池パネル
１４ シリカ膜
１５ 水酸基
１６ メチルシリル基
DESCRIPTION OF
11 Water / oil repellent antifouling composite film
12 solar cells
13 Solar cell panel having a water / oil / oil / antifouling coating formed on the light
Claims (23)
The method for manufacturing a solar energy utilization device according to claim 12, wherein after the formation of the composite film, the solar cell is treated with a solution in which a substance containing a methylsilyl group is dissolved.
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| JP2012158100A (en) * | 2011-02-01 | 2012-08-23 | Seiko Epson Corp | Method for manufacturing nozzle plate, and liquid ejection head |
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| JP5589215B2 (en) | 2014-09-17 |
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