JP2008222842A - Coating agent for forming photocatalyst coating film and method for forming photocatalyst coating film - Google Patents
Coating agent for forming photocatalyst coating film and method for forming photocatalyst coating film Download PDFInfo
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- JP2008222842A JP2008222842A JP2007062172A JP2007062172A JP2008222842A JP 2008222842 A JP2008222842 A JP 2008222842A JP 2007062172 A JP2007062172 A JP 2007062172A JP 2007062172 A JP2007062172 A JP 2007062172A JP 2008222842 A JP2008222842 A JP 2008222842A
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- coating film
- photocatalyst
- titanium oxide
- photocatalyst coating
- coating agent
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- 239000011248 coating agent Substances 0.000 title claims abstract description 154
- 238000000576 coating method Methods 0.000 title claims abstract description 118
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 65
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010419 fine particle Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 abstract description 16
- -1 titanium alkoxide Chemical class 0.000 abstract description 11
- 239000010936 titanium Substances 0.000 abstract description 8
- 229910052719 titanium Inorganic materials 0.000 abstract description 8
- 238000004528 spin coating Methods 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 100
- 239000011521 glass Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000002135 nanosheet Substances 0.000 description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- RLDQYSHDFVSAPL-UHFFFAOYSA-L calcium;dithiocyanate Chemical compound [Ca+2].[S-]C#N.[S-]C#N RLDQYSHDFVSAPL-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- UKGZHELIUYCPTO-UHFFFAOYSA-N dicesium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Cs+].[Cs+] UKGZHELIUYCPTO-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SDUJOOJUQMRDAX-UHFFFAOYSA-N ethanol;thiourea Chemical class CCO.NC(N)=S SDUJOOJUQMRDAX-UHFFFAOYSA-N 0.000 description 1
- XJFYWGIWEYQMPK-UHFFFAOYSA-N ethanol;urea Chemical compound CCO.NC(N)=O XJFYWGIWEYQMPK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- YQXQWFASZYSARF-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC YQXQWFASZYSARF-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- MWCGLTCRJJFXKR-UHFFFAOYSA-N n-phenylethanethioamide Chemical compound CC(=S)NC1=CC=CC=C1 MWCGLTCRJJFXKR-UHFFFAOYSA-N 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-N tetrabutylazanium;hydrochloride Chemical compound Cl.CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
本発明は、例えば、ガラス、プラスチック、金属、セラミックス等から成る部材の表面に光触媒塗膜を形成することができるコーティング剤、光触媒塗膜、及び光触媒塗膜形成方法に関する。 The present invention relates to a coating agent, a photocatalytic coating film, and a photocatalytic coating film forming method capable of forming a photocatalytic coating film on the surface of a member made of glass, plastic, metal, ceramics, or the like.
酸化チタン光触媒は、そのバンドギャップに相当するエネルギー（紫外光）を吸収し、価電子帯の電子が伝導帯に励起され、価電子帯には電子の抜け殻である正孔（ホール：h+）が、伝導帯には電子（e-）が生じる。この電子とホールは酸化チタン表面の水や酸素と反応して極めて強い酸化力を有するラジカルを生成し、そのラジカルは汚れやバクテリアを構成するほとんど全ての有機物を分解することができる。また、酸化チタンの表面は、紫外光照射によって高度に親水化した光誘起超親水性を示すことから、光によって汚れを分解し、且つ水で汚れを洗い流して常に清浄な表面を保つセルフクリーニング材料として実用化されている。
酸化チタン光触媒は、一般的には、基材の表面に塗膜として形成されるが、その形成方法としては、バインダー成分を含む光触媒粒子の懸濁液をコーティングし、乾燥させる方法がある。バインダーは塗装される基材の種類によって選択され、シリカやケイ酸塩などの無機系バインダー、或いはシリコーン樹脂やフッ素樹脂などの酸化チタンの光触媒反応に侵されにくい有機系バインダーが利用されている。
従来の酸化チタン光触媒の課題としては、
（１）強い紫外光の下では光触媒活性が発現するものの、可視光領域の光や、屋内や室内蛍光灯レベルの微弱な紫外光では十分な光触媒活性を示さない。
（２）塗膜と基材との十分な密着強度、および塗膜の十分な硬度が得られず、適用範囲が限られる。例えば、洗車機にかけることが前提となる車両用の窓ガラス等には適用できない。
というものがある。
The titanium oxide photocatalyst absorbs energy (ultraviolet light) corresponding to its band gap, and electrons in the valence band are excited to the conduction band, and holes (holes: h + ) that are shells of electrons in the valence band. There, the electrons in the conduction band (e -) occurs. These electrons and holes react with water and oxygen on the surface of titanium oxide to generate radicals having extremely strong oxidizing power, and the radicals can decompose almost all organic substances constituting dirt and bacteria. In addition, since the surface of titanium oxide exhibits light-induced super-hydrophilicity that has been made highly hydrophilic by ultraviolet light irradiation, it is a self-cleaning material that decomposes dirt by light and keeps the surface clean by washing off dirt with water. Has been put to practical use.
The titanium oxide photocatalyst is generally formed as a coating film on the surface of the substrate. As a method for forming the titanium oxide photocatalyst, there is a method in which a suspension of photocatalyst particles containing a binder component is coated and dried. The binder is selected depending on the type of substrate to be coated, and an inorganic binder such as silica or silicate, or an organic binder that is not easily affected by the photocatalytic reaction of titanium oxide such as silicone resin or fluororesin is used.
As problems of conventional titanium oxide photocatalysts,
(1) Although photocatalytic activity is exhibited under intense ultraviolet light, sufficient photocatalytic activity is not exhibited with light in the visible light region or weak ultraviolet light at the level of indoor or indoor fluorescent lamps.
(2) A sufficient adhesion strength between the coating film and the substrate and a sufficient hardness of the coating film cannot be obtained, and the application range is limited. For example, it cannot be applied to a window glass for a vehicle that is premised on being applied to a car wash.
There is something called.
上記（１）の課題に関し、酸化チタンに窒素を微量ドーピングすることで、可視光領域での吸収が得られるようになり、条件を最適化すれば、可視光のみで親水化反応を進めることができる技術が開示されている（特許文献１参照）。また、上記（２）の課題に関し、酸化チタンゾルと安定化チタンアルコキシドとを含有して成る酸化チタン薄膜形成用組成物をガラスに塗布し、３５０〜７００℃で焼成することで、機械的耐久性を高める技術が開示されている（特許文献２参照）。
しかしながら、特許文献１の技術は、ドーピングにより構造中に歪を導入することが避けられず、結果として可視光領域での反応性を付与できるものの、微弱な紫外光に対する感度は得られなくなる。また、特許文献２の技術で報告されている機械的耐久性は、ＪＩＳ−Ｋ５４００で規定される鉛筆引っかき試験において７Ｈに過ぎず、車両用等の用途に適用できる耐久性を有していない。 However, the technique of Patent Document 1 inevitably introduces strain into the structure by doping, and as a result, it is possible to impart reactivity in the visible light region, but sensitivity to weak ultraviolet light cannot be obtained. Moreover, the mechanical durability reported by the technique of patent document 2 is only 7H in the pencil scratch test prescribed | regulated by JIS-K5400, and does not have the durability applicable to uses, such as a vehicle.
本発明は以上の点に鑑みなされたものであり、可視光及び微弱な紫外光の下で光触媒活性を示し、耐久性が高い光触媒塗膜、光触媒塗膜の形成に用いられるコーティング剤、及び光触媒塗膜形成方法を提供することを目的とする。 The present invention has been made in view of the above points, and exhibits photocatalytic activity under visible light and weak ultraviolet light, and has high durability. Photocatalytic coating film, coating agent used for formation of photocatalytic coating film, and photocatalyst It aims at providing the coating-film formation method.
（１）請求項１の発明は、
鱗片状の酸化チタン微粒子と、
含硫黄化合物と、
を含むコーティング剤を要旨とする。
(1) The invention of claim 1
Scaly titanium oxide particles,
A sulfur-containing compound;
The gist is a coating agent containing
本発明のコーティング剤を塗布することによって形成した塗膜は、可視光及び微弱な紫外光で光触媒活性を有する。
また、本発明のコーティング剤を塗布することによって形成した塗膜は、図１に示すように、塗膜１の中で、鱗片状（シート状）の酸化チタン粒子５が一定の配向性をもって積層した微細構造を有し、平滑性が高い。そのため、高い平滑性と密着性を持つ塗膜を形成できる。そして、塗膜の平滑性が高いことにより、塗膜の表面積が小さくなり、塗膜への汚染物質の付着量が少なくなる。そして、たとえ汚れが塗膜の表面に付着しても酸化チタンの光触媒活性および超親水性により汚れの分解・除去が可能である。更に、塗膜硬度も高い。
The coating film formed by applying the coating agent of the present invention has photocatalytic activity under visible light and weak ultraviolet light.
In addition, as shown in FIG. 1, the coating film formed by applying the coating agent of the present invention is laminated with scale-like (sheet-like) titanium oxide particles 5 in a certain orientation in the coating film 1. It has a fine structure and high smoothness. Therefore, a coating film having high smoothness and adhesion can be formed. And since the smoothness of a coating film is high, the surface area of a coating film becomes small and the adhesion amount of the contaminant to a coating film decreases. Even if dirt adheres to the surface of the coating film, the dirt can be decomposed and removed by the photocatalytic activity and super hydrophilicity of titanium oxide. Furthermore, the coating film hardness is also high.
また、本発明のコーティング剤を塗布することにより形成した塗膜は、鱗片状の酸化チタン粒子が一定の配向性をもって積層した微細構造を有しているので、球状の酸化チタン粒子が分散した構造に比べて、塗膜を超薄膜化することが可能である。 Moreover, since the coating film formed by applying the coating agent of the present invention has a fine structure in which scaly titanium oxide particles are laminated with a certain orientation, a structure in which spherical titanium oxide particles are dispersed Compared to the above, it is possible to make the coating film ultra-thin.
更に、本発明では、酸化チタンが薄く広げられたシート状（鱗片状）であるので、酸化チタンの単位体積あたりの表面積が大きい。そのため、本発明のコーティング剤を用いて形成された塗膜では、基材（コーティング剤を塗布する対象）と酸化チタンとの接触面積が大きく、塗膜の密着性が高い。 Furthermore, in the present invention, the surface area per unit volume of the titanium oxide is large because the titanium oxide is in the form of a thin sheet (scale-like). Therefore, in the coating film formed using the coating agent of this invention, the contact area of a base material (object which apply | coats a coating agent) and titanium oxide is large, and the adhesiveness of a coating film is high.
また、本発明のコーティング剤は、スピンコート法などにより、簡便に広い面積にわたって塗膜を形成することができる。
また、本発明のコーティング剤を用いて形成した塗膜は、超親水性を示すので、その表面に水が付着しても水滴となりにくい。そのため、防曇性において優れている。
In addition, the coating agent of the present invention can easily form a coating film over a wide area by a spin coating method or the like.
Moreover, since the coating film formed using the coating agent of this invention shows super hydrophilicity, even if water adheres to the surface, it is hard to become a water droplet. Therefore, it is excellent in antifogging properties.
前記鱗片状の酸化チタン微粒子の大きさは０．１〜２０μｍの範囲が好適であり、その厚みは０．３〜３ｎｍの範囲が好適であり、更に望ましくは０．５〜１ｎｍの範囲が好適である。また、鱗片状の酸化チタン微粒子におけるアスペクト比は１００〜５０００の範囲が好適である。前記鱗片状の酸化チタン微粒子としては、例えば、層状のチタン酸塩が単層まで剥離したシート状の粒子が挙げられる。コーティング剤に占める鱗片状の酸化チタン微粒子の割合は、０．１〜１０重量％の範囲が好適である。 The size of the scaly titanium oxide fine particles is preferably in the range of 0.1 to 20 μm, and the thickness is preferably in the range of 0.3 to 3 nm, and more preferably in the range of 0.5 to 1 nm. It is. The aspect ratio of the scale-like titanium oxide fine particles is preferably in the range of 100 to 5000. Examples of the scaly titanium oxide fine particles include sheet-like particles in which a layered titanate is peeled up to a single layer. The ratio of the flaky titanium oxide fine particles in the coating agent is preferably in the range of 0.1 to 10% by weight.
本発明のコーティング剤に含まれる溶媒としては、例えば、エステル類、ケトン類、アルコール類等があり、具体的には、酢酸エチル、酢酸イソブチル、アセトン、メチルエチルケトン、メタノール、エタノール、イソプロパノール等が挙げられ、特にアルコール類が好ましい。 Examples of the solvent contained in the coating agent of the present invention include esters, ketones, alcohols, and the like. Specific examples include ethyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, and the like. In particular, alcohols are preferred.
前記含硫黄化合物は、硫黄を含む化合物が広く該当し、例えば、チオエーテル類、チオ尿素類、チオアミド類、チオアルコール類、チオアルデヒド類、チアジル類、メルカプタール類、チオール類、チオシアン酸塩類等があり、具体的な化合物としては、チオフェノール、チオフェン、ベンゾチオフェン、チオベンゾフェン、ジベンゾチオフェン、ビチオフェン、フェノチアジン、スルホラン、チアジン、チアゾール、チアジアゾール、チアゾ
リン、チアゾリジン、チアントレン、チアン、チオアセトアニリド、チオアセトアミド、チオベンズアミド、チオアニソール、チオニン、メチルチオール、チオエーテル、チオシアン、チオ尿素等が挙げられ、特に、酸素を含まず硫黄、窒素、及び炭素を有する化合物（例えばチオ尿素）が好ましい。
The sulfur-containing compounds widely include compounds containing sulfur, such as thioethers, thioureas, thioamides, thioalcohols, thioaldehydes, thiazyl, mercaptals, thiols, and thiocyanates. Specific compounds include thiophenol, thiophene, benzothiophene, thiobenzophene, dibenzothiophene, bithiophene, phenothiazine, sulfolane, thiazine, thiazole, thiadiazole, thiazoline, thiazolidine, thianthrene, thiane, thioacetanilide, thioacetamide, thio Examples include benzamide, thioanisole, thionine, methylthiol, thioether, thiocyan, thiourea, and the like, and particularly, a compound having no oxygen, sulfur, nitrogen, and carbon (for example, thiourea) is preferable.
本発明のコーティング剤は、バインダーを配合することができる（図１における７参照）。このバインダーとしては、例えば、アセチルアセトンで安定化させたチタンアルコキシド（例えば、チタン（ＩＶ）イソブトキシド、チタン（ＩＶ）イソプロポキシド、チタン（ＩＶ）エトキシド、チタンテトラ（ＩＶ）ブトキシド、チタン（ＩＶ）ｔ−ブトキシド、チタン（ＩＶ）ｎ−プロポキシド、チタン（ＩＶ）メトキシド等）、テトラアルコキシシランから調製される酸化ケイ素のゾル、チタンテトラアルコキシドから調製される酸化チタンのゾル等が挙げられる。 The coating agent of this invention can mix | blend a binder (refer 7 in FIG. 1). Examples of the binder include titanium alkoxide stabilized with acetylacetone (for example, titanium (IV) isobutoxide, titanium (IV) isopropoxide, titanium (IV) ethoxide, titanium tetra (IV) butoxide, titanium (IV)). t-butoxide, titanium (IV) n-propoxide, titanium (IV) methoxide, etc.), silicon oxide sol prepared from tetraalkoxysilane, titanium oxide sol prepared from titanium tetraalkoxide, and the like.
これらのバインダーを含有することにより、鱗片状の酸化チタン微粒子と基材との密着性を高めることができ、樹脂バインダーを含有する場合に比べて、化学的安定性や物理的安定性において優れている。また、これらのバインダーを含有する場合は、樹脂バインダーを含む場合とは異なり、低い焼成温度下でも、無機物質を主成分とする（あるいは無機物質の組成のみから成る）塗膜を形成することができる。そのため、熱に弱い樹脂等にも硬い塗膜を形成することができる。 By containing these binders, the adhesion between the scaly titanium oxide fine particles and the substrate can be improved, and in terms of chemical stability and physical stability, compared to the case of containing a resin binder. Yes. Further, when these binders are contained, unlike the case where resin binders are contained, it is possible to form a coating film containing an inorganic substance as a main component (or comprising only the composition of an inorganic substance) even at a low firing temperature. it can. Therefore, a hard coating film can be formed even on a resin that is vulnerable to heat.
コーティング剤全量に対するチタンアルコキシドの重量比は、１〜９０（好ましくは５〜９０）重量％の範囲が好適である。５重量％以上であることにより、非常に硬い塗膜を形成することができる。また、９０重量％以下であることにより光触媒活性と平滑性の点で有利である。コーティング剤全量に対する酸化ケイ素の重量比は、１〜５０重量％の範囲が好適である。５重量％以上であることにより、非常に硬い塗膜を形成することができる。また、２５重量％以下であることにより光触媒活性と平滑性の点で有利である。コーティング剤全量に対する酸化チタンゾルの重量比は、５〜５０重量％の範囲が好適である。２０重量％以上であることにより、膜硬度の点で有利である。また、４０重量％以下であることにより平滑性の点で有利である。 The weight ratio of the titanium alkoxide with respect to the total amount of the coating agent is preferably in the range of 1 to 90 (preferably 5 to 90)% by weight. By being 5% by weight or more, a very hard coating film can be formed. Moreover, it is advantageous in terms of photocatalytic activity and smoothness by being 90% by weight or less. The weight ratio of silicon oxide to the total amount of the coating agent is preferably in the range of 1 to 50% by weight. By being 5% by weight or more, a very hard coating film can be formed. Further, the content of 25% by weight or less is advantageous in terms of photocatalytic activity and smoothness. The weight ratio of the titanium oxide sol with respect to the total amount of the coating agent is preferably in the range of 5 to 50% by weight. By being 20% by weight or more, it is advantageous in terms of film hardness. Moreover, it is advantageous at the point of smoothness by being 40 weight% or less.
尚、本発明のコーティング剤は、板状のナノシートを用いることにより、球状の酸化チタン微粒子を用いる場合に比べて、バインダーの割合が少なくても硬い塗膜を形成することができる。つまり、従来のコーティング剤では、通常、バインダーを５０重量％ほど配合していたが、本発明では、上述した含有量でよいため、非常に硬い塗膜を形成することができる。 In addition, the coating agent of this invention can form a hard coating film by using a plate-shaped nanosheet, even if there are few ratios of a binder compared with the case where spherical titanium oxide microparticles are used. That is, in the conventional coating agent, the binder is usually blended by about 50% by weight. However, in the present invention, since the above-described content is sufficient, a very hard coating film can be formed.
本発明のコーティング剤は、例えば、溶媒に含硫黄化合物、バインダー、ポリエチレングリコールを加えて完全な一液溶液になるまで撹拌し、次に、薄片状の酸化チタン粒子（チタニアナノシート）を分散させた溶液を所定の割合で加えて混合するという方法で製造できる。このとき、必ずしもポリエチレングリコールを加える必要はない。ポリエチレングリコールを加える場合は、コーティング剤に対して２０重量％を超えない範囲が好ましく、１５〜１８重量％の範囲が特に好ましい。加えるチオ尿素のモル量は、薄片状の酸化チタン粒子（チタニアナノシート）とバインダーの総モル量に対して４倍を超えない範囲が好ましい。
（２）請求項２の発明は、
前記含硫黄化合物がチオ尿素であることを特徴とする請求項１記載のコーティング剤を要旨とする。
In the coating agent of the present invention, for example, a sulfur-containing compound, a binder, and polyethylene glycol are added to a solvent and stirred until a complete one-component solution is obtained, and then flaky titanium oxide particles (titania nanosheets) are dispersed. It can be produced by a method in which a solution is added at a predetermined ratio and mixed. At this time, it is not always necessary to add polyethylene glycol. When adding polyethylene glycol, the range which does not exceed 20 weight% with respect to a coating agent is preferable, and the range of 15-18 weight% is especially preferable. The molar amount of thiourea to be added is preferably within a range not exceeding 4 times the total molar amount of flaky titanium oxide particles (titania nanosheets) and binder.
(2) The invention of claim 2
The gist of the coating agent according to claim 1, wherein the sulfur-containing compound is thiourea.
本発明のコーティング剤を塗布することによって形成した塗膜は、可視光及び微弱な紫外光の下で、一層高い光触媒活性を有する。
（３）請求項３の発明は、
請求項１又は２に記載のコーティング剤を塗布する塗布工程と、
塗布された前記コーティング剤を乾燥させる乾燥工程と、を有することを特徴とする光触媒塗膜の形成方法を要旨とする。
The coating film formed by applying the coating agent of the present invention has higher photocatalytic activity under visible light and weak ultraviolet light.
(3) The invention of claim 3
An application step of applying the coating agent according to claim 1 or 2,
And a drying step of drying the applied coating agent. The gist of the method is to form a photocatalyst coating film.
本発明で得られた光触媒塗膜は、可視光及び微弱な紫外光で、一層高い光触媒活性を有する。また、本発明で得られた光触媒塗膜は、球状微粒子の酸化チタンを分散して成るコーティング剤を用いる場合と比べて、高い平滑性と密着性を持つ。そのため、そもそも汚れが付着しにくい防汚性を有しており、たとえ汚れが付着しても酸化チタンの光触媒活性および超親水性により分解・除去が可能である。 The photocatalyst coating film obtained in the present invention has higher photocatalytic activity under visible light and weak ultraviolet light. Moreover, the photocatalyst coating film obtained by the present invention has higher smoothness and adhesion than the case of using a coating agent formed by dispersing spherical fine titanium oxide. Therefore, it originally has antifouling properties that make it difficult for dirt to adhere to it, and even if dirt adheres, it can be decomposed and removed by the photocatalytic activity and superhydrophilicity of titanium oxide.
更に、本発明では、酸化チタンが薄く広げられたシート状であるので、酸化チタンの単位体積あたりの表面積が大きい。そのため、本発明で形成された光触媒塗膜では、基板と酸化チタンとの接触面積が大きく、光触媒塗膜の密着性が高い。 Furthermore, in the present invention, the surface area per unit volume of the titanium oxide is large because the titanium oxide is in the form of a thin sheet. Therefore, in the photocatalyst coating film formed by this invention, the contact area of a board | substrate and a titanium oxide is large, and the adhesiveness of a photocatalyst coating film is high.
前記塗布工程においてコーティング剤を塗布する方法としては、例えば、スピンコート、プレートコート、ディップコート、スプレーコートなど、一般的にウェット法に用いられるコーティング手法が利用できる。そして、コーティングした後、乾燥し、焼成を行う。
（４）請求項４の発明は、
前記乾燥工程において４００〜６００℃の温度に加熱することを特徴とする請求項３に記載の光触媒塗膜の形成方法を要旨とする。
As a method for applying the coating agent in the application step, for example, a coating method generally used in a wet method such as spin coating, plate coating, dip coating, spray coating, or the like can be used. And after coating, it dries and performs baking.
(4) The invention of claim 4
The gist of the method for forming a photocatalyst coating film according to claim 3, wherein heating is performed at a temperature of 400 to 600 ° C. in the drying step.
本発明では、上記の温度で加熱することにより、形成された光触媒塗膜の、可視光及び微弱な紫外光の下での光触媒活性が一層高くなる。
また、本発明では、乾燥工程において加熱を行うことにより、乾燥に要する時間を短縮でき、形成される塗膜の硬度を向上させることができる。加熱時間は３０秒〜４時間の範囲が好適であり、特に３０分〜３時間の範囲が好ましい。
（５）請求項５の発明は、
請求項３又は４に記載の光触媒塗膜の形成方法によって形成される光触媒塗膜を要旨とする。
In the present invention, by heating at the above temperature, the photocatalytic activity of the formed photocatalytic coating film under visible light and weak ultraviolet light is further increased.
Moreover, in this invention, the time which drying requires can be shortened by heating in a drying process, and the hardness of the coating film formed can be improved. The heating time is preferably in the range of 30 seconds to 4 hours, particularly preferably in the range of 30 minutes to 3 hours.
(5) The invention of claim 5
The gist is a photocatalyst coating film formed by the method for forming a photocatalyst coating film according to claim 3.
本発明の光触媒塗膜は、可視光及び微弱な紫外光で光触媒活性を有する。また、本発明の光触媒塗膜では、酸化チタンが薄く広げられたシート状（鱗片状）であるので、酸化チタンの単位体積あたりの表面積が大きい。そのため、基材と酸化チタンとの接触面積が大きく、光触媒塗膜の密着性が高い。また、酸化チタンと汚染物質との接触面積も大きくなるので、汚れの分解・除去の能力も高い。また、本発明の光触媒塗膜は、超親水性を示すので、その表面に水が付着しても水滴となりにくい。そのため、防曇性において優れている。
（６）請求項６の発明は、
前記鱗片状の酸化チタン微粒子が一定の配向性をもって積層した微細構造を有することを特徴とする請求項５に記載の光触媒塗膜を要旨とする。
The photocatalyst coating film of the present invention has photocatalytic activity under visible light and weak ultraviolet light. Moreover, in the photocatalyst coating film of this invention, since the titanium oxide is the sheet form (scale shape) which was spread thinly, the surface area per unit volume of a titanium oxide is large. Therefore, the contact area of a base material and a titanium oxide is large, and the adhesiveness of a photocatalyst coating film is high. In addition, since the contact area between the titanium oxide and the contaminant is increased, the ability to decompose and remove dirt is high. Moreover, since the photocatalyst coating film of this invention shows super hydrophilicity, even if water adheres to the surface, it is hard to become a water droplet. Therefore, it is excellent in antifogging properties.
(6) The invention of claim 6
The gist of the photocatalyst coating film according to claim 5, wherein the scaly titanium oxide fine particles have a fine structure in which the fine particles are laminated with a certain orientation.
本発明の光触媒塗膜は、鱗片状の酸化チタン粒子が一定の配向性をもって積層した微細構造を有し、平滑性が高い。そのため、汚れが付着しにくい防汚性を有しており、たとえ汚れが付着しても酸化チタンの光触媒活性および超親水性により分解・除去が可能である。更に、塗膜硬度も高い。 The photocatalytic coating film of the present invention has a fine structure in which scaly titanium oxide particles are laminated with a certain orientation, and has high smoothness. Therefore, it has antifouling properties that prevent dirt from adhering, and even if dirt adheres, it can be decomposed and removed by the photocatalytic activity and superhydrophilicity of titanium oxide. Furthermore, the coating film hardness is also high.
また、本発明の光触媒塗膜は、上記の微細構造を有しているので、球状の酸化チタン粒
子が分散した構造に比べて、膜厚を超薄膜可することが可能である。
（７）請求項７の発明は、
基材と、当該基材の表面に形成された請求項５又は６記載の光触媒塗膜とを有する光触媒塗膜具有製品を要旨とする。
本発明の光触媒塗膜具有製品は、請求項５又は６記載の光触媒塗膜を備えることにより、可視光及び微弱な紫外光で光触媒活性を有する。また、本発明の光触媒塗膜具有製品は、その表面の平滑性、防汚性が高く、たとえ汚れが付着しても酸化チタンの光触媒活性および超親水性により分解・除去が可能である。また、本発明の光触媒塗膜具有製品は、光触媒塗膜と基材との密着性が高く、また、光触媒塗膜が超親水性を示すので、その表面に水が付着しても水滴となりにくく、防曇性において優れている。
本発明において適用できる基材としては、酸化チタンがアナターゼに結晶化するために必要な焼成に耐えられる物質から成るものが好ましく、例えばガラス、金属、セラミックス、耐熱性高分子（例えば、エポキシ樹脂、ポリイミド樹脂、珪素系高分子、フェノール樹脂等）などが挙げられる。また、例えば、光触媒塗膜の形成にディッピングなどの方法を用いれば、基材の形状に関する制約はない。
In addition, since the photocatalyst coating film of the present invention has the above-mentioned fine structure, it can be made ultrathin as compared with a structure in which spherical titanium oxide particles are dispersed.
(7) The invention of claim 7
The gist is a product having a photocatalyst coating film having a base material and the photocatalyst coating film according to claim 5 or 6 formed on the surface of the base material.
The product with a photocatalyst coating film according to the present invention has a photocatalytic activity with visible light and weak ultraviolet light by including the photocatalyst coating film according to claim 5 or 6. Further, the product with a photocatalyst coating film of the present invention has high surface smoothness and antifouling properties, and even if dirt is attached, it can be decomposed and removed by the photocatalytic activity and superhydrophilicity of titanium oxide. In addition, the photocatalyst coating-equipped product of the present invention has high adhesion between the photocatalyst coating film and the substrate, and the photocatalyst coating film exhibits super hydrophilicity, so even if water adheres to the surface, it is difficult to form water droplets. Excellent in antifogging property.
The base material applicable in the present invention is preferably made of a material that can withstand the firing required for crystallization of titanium oxide to anatase. For example, glass, metal, ceramics, heat-resistant polymer (for example, epoxy resin, Polyimide resin, silicon polymer, phenol resin, etc.). For example, if a method such as dipping is used to form the photocatalyst coating film, there is no restriction on the shape of the substrate.
本発明の光触媒塗膜具有製品としては、例えば、基体がガラスであるガラス製品、基体が金属である金属製品、基体がセラミックスであるセラミックス製品、基体が耐熱性プラスチックである耐熱性プラスチック製品等が挙げられる。上記ガラス製品の例としては、例えば、自動車用ガラス、鉄道車両用ガラス、建材用ガラス、光学ガラス、照明用ガラス、鏡面用ガラス、ショーケース、食品保存用ガラス容器、太陽電池カバーガラス、水槽用ガラス等が挙げられる。上記金属製品の例としては、例えば、門扉、鉄柵、鉄道車両無塗装外板、航空機外板、アルミホイール、アルミ建材、ステンレス建材等が挙げられる。上記セラミックス製品の例としては、例えば、碍子、タイル、食器、衛生用品、瓦等が挙げられる。上記耐熱性プラスチック製品の例としては、例えば、自動車部品用プラスチック、加熱調理器具用樹脂部品、高出力モーター用カバー、絶縁用樹脂部品等が挙げられる。 Examples of the product with a photocatalyst coating film of the present invention include a glass product whose base is glass, a metal product whose base is metal, a ceramic product whose base is ceramic, and a heat-resistant plastic product whose base is a heat-resistant plastic. Can be mentioned. Examples of the glass products include, for example, glass for automobiles, glass for railway vehicles, glass for building materials, optical glass, glass for lighting, glass for mirror surfaces, showcases, glass containers for food preservation, solar cell cover glasses, and water tanks. Glass etc. are mentioned. Examples of the metal products include gates, iron fences, railcar unpainted skins, aircraft skins, aluminum wheels, aluminum building materials, and stainless steel building materials. Examples of the ceramic product include insulators, tiles, tableware, sanitary goods, and tiles. Examples of the heat-resistant plastic products include plastics for automobile parts, resin parts for cooking utensils, high-power motor covers, insulating resin parts, and the like.
本発明を実施例に基づいて説明する。 The present invention will be described based on examples.
ａ）チタニアナノシートの製造
炭酸セシウム、酸化チタンをモル比１：５．３の割合で混合し、８００℃、２０時間の焼成を２回行った。生成したチタン酸セシウムを希塩酸中で撹拌、ろ過、乾燥するという一連の処理を４回繰り返し、セシウムイオンを水素イオンに置き換えた層状チタン酸を得た。これに、テトラブチルアンモニウム塩酸塩水溶液を加え、１４日間撹拌してチタニアナノシートを調製した。
a) Production of titania nanosheet Cesium carbonate and titanium oxide were mixed at a molar ratio of 1: 5.3, and baked at 800 ° C. for 20 hours twice. A series of treatments of stirring, filtering and drying the produced cesium titanate in dilute hydrochloric acid was repeated four times to obtain layered titanic acid in which cesium ions were replaced with hydrogen ions. Tetrabutylammonium hydrochloride aqueous solution was added to this, and it stirred for 14 days, and prepared the titania nanosheet.
ｂ）コーティング剤の調製
チオ尿素３．０５ｇを量りとり、エタノール１００ｍｌへ入れて超音波洗浄機で１０分間、マグネティックスターラーで３０分間それぞれ撹拌してチオ尿素を完全に溶解し、０．４Ｍのチオ尿素エタノール溶液とした。このチオ尿素エタノール溶液１１．５ｍｌ、ポリエチレングリコール３．４ｍｌ、予めアセチルアセトンで安定化させたチタンアルコキシド３．３３ｍｌ、及び前記ａ）で製造したチタニアナノシートを分散させたエタノール溶液（チタニアナノシートの濃度１重量％）５ｍｌを、それぞれ量りとり、ビーカーに入れてマグネティックスターラーで３０分間撹拌してコーティング溶液を調製した。
b) Preparation of coating agent 3.05 g of thiourea was weighed, put into 100 ml of ethanol, stirred for 10 minutes with an ultrasonic cleaner and 30 minutes with a magnetic stirrer to completely dissolve thiourea, and 0.4 M thiol A urea ethanol solution was used. 11.5 ml of this thiourea ethanol solution, 3.4 ml of polyethylene glycol, 3.33 ml of titanium alkoxide previously stabilized with acetylacetone, and an ethanol solution in which the titania nanosheet produced in a) is dispersed (concentration of titania nanosheet 1 weight) %) 5 ml each was weighed, placed in a beaker and stirred with a magnetic stirrer for 30 minutes to prepare a coating solution.
ｃ）光触媒塗膜の形成
前記ｂ）で調製したコーティング溶液を、予め洗浄しておいたパイレックス（登録商標）ガラス上にスピンコート法（１０００ｒｐｍ、２０秒）で塗布、乾燥してから、４５０
℃で３時間焼成することで、光触媒塗膜を形成した。
（比較例１）
エタノール溶液１１．５ｍｌ、ポリエチレングリコール３．４ｍｌ、予めアセチルアセトンで安定化させたチタンアルコキシド６５μｌ、及び前記実施例１のａ）で製造したチタニアナノシートを分散させた溶液（チタニアナノシートの濃度１重量％）５ｍｌをそれぞれ量りとり、ビーカーに入れてマグネティックスターラーで３０分間撹拌してコーティング溶液を調製した。その後、予め洗浄しておいたパイレックス（登録商標）ガラス上にコーティング溶液をスピンコート法（１０００ｒｐｍ、２０秒）で塗布、乾燥してから、４５０℃で３時間焼成することで、光触媒塗膜を形成した。
（比較例２）
市販されている、高温焼付けゾル・ゲルタイプの光触媒コーティング剤（日本曹達(株)
ビストレイターＨ 光触媒コーティング ＮＤＨ−５１０Ｃ）をパイレックス（登録商標）ガラス上にスピンコート法（１０００ｒｐｍ、２０秒）で塗布、乾燥してから、４５０℃で３時間焼成することで、光触媒塗膜を形成した。
（効果を確かめるための試験）
(i)可視光吸収特性
実施例１、及び比較例１で製造した光触媒塗膜の可視光吸収特性を紫外可視分光光度計（(株)日立ハイテクノロジーズ製：Ｕ−３３１０）にて測定した。その結果を図２に示す。図２から明らかなとおり、実施例１で製造した光触媒塗膜は、比較例１で製造した光触媒塗膜に比べて可視光領域での吸収が遙かに高い。この結果は、実施例１で製造した光触媒塗膜が可視光領域で光触媒活性を有することを裏付けている。
(ii) 光触媒塗膜の硬度
実施例１、及び比較例２で製造した光触媒塗膜の塗膜硬度を、「ＪＩＳ−Ｋ５４００」における鉛筆引っかき試験の方法に準じて測定した。その結果、実施例１で製造した光触媒塗膜の塗膜硬度は９Ｈ以上であり、非常に高かった。一方、比較例２で製造した光触媒塗膜の塗膜硬度は６Ｂであった。
(iii)塗膜の平滑度
実施例１、及び比較例２で製造した光触媒塗膜の表面を、走査型プローブ顕微鏡（日本電子(株)製：ＪＳＰＭ−５２００）を用いて測定した。測定条件は、タッピングモードとした。実施例１で製造した光触媒塗膜の表面観察画像を図３（ａ）に示し、比較例２で製造した光触媒塗膜の表面観察画像を図３（ｂ）に示す。図３（ａ）から明らかなとおり、実施例１で製造した光触媒塗膜は非常に緻密で平滑となっており、表面粗さＲａは２．１ｍｍであった。一方、図３（ｂ）から明らかなとおり、比較例２で製造した光触媒塗膜の表面は凹凸が大きくなっており、表面粗さは９．２ｎｍであった。
(iv)防汚性
汚れのモデル物質であるメチレンブルー水溶液（濃度が０．０１Ｍ）を調製し、このメチレンブルー水溶液に、実施例１で光触媒塗膜を形成したガラス片、及び比較例２で光触媒塗膜を形成したガラス片をそれぞれ１２時間浸漬した。引き上げたガラス片を水洗したのち、紫外可視分光光度計（(株)日立ハイテクノロジーズ製：Ｕ−３３１０）にて光触媒塗膜に付着したメチレンブルーの吸収スペクトルを測定した。その結果を図４に示す。
図４から明らかなとおり、実施例１で製造した光触媒塗膜は、比較例２で製造した光触媒塗膜よりも吸収スペクトルのピークが小さい。このことから、実施例１で製造した光触媒塗膜は、焼成することによって非常に緻密で平滑な塗膜となっており、メチレンブルーが塗膜内部に侵入し難く、且つ付着し難いことが分かる。
(v)微弱な紫外光照射時の光誘起親水性
実施例１、及び比較例１で製造した光触媒塗膜のそれぞれについて、室内蛍光灯レベル
に近い５μＷ／ｃｍ2の強度で所定時間紫外光照射を行い、その直後に接触角計（dataphysics社製：ＯＣＡ１５plus）を用いて水の接触角を測定した。測定は、照射時間を変えながら、繰り返し行った。その結果を図５に示す。図５から明らかなとおり、実施例１で製造した光触媒塗膜は、照射１０分で接触角が１０度以下となるまで親水化し、照射２０分では、接触角が０度である超親水性状態を示した。一方、比較例１で製造した光触媒塗膜は、照射１００分後でも接触角が１０度以上であった。
(vi)可視光照射時の光誘起親水性
次に、前記(v)の実験方法を基本としつつ、光源を蛍光灯とし、また、４２０ｎｍ以下の波長をカットするフィルターを光源に装着して試験を行った。その結果を図６に示す。図６から明らかなとおり、実施例１で製造した光触媒塗膜は、照射１０時間で接触角が１０度付近となるまで親水化し、照射３５時間後に接触角が１０度以下となった。一方、比較例１で製造した光触媒塗膜は、照射３５時間後でも、接触角が４５度以上であり、ほとんど親水化しなかった。
c) Formation of photocatalyst coating film The coating solution prepared in the above b) was applied to a pre-cleaned Pyrex (registered trademark) glass by a spin coating method (1000 rpm, 20 seconds) and dried, then 450
The photocatalyst coating film was formed by baking at 3 degreeC for 3 hours.
(Comparative Example 1)
11.5 ml of ethanol solution, 3.4 ml of polyethylene glycol, 65 μl of titanium alkoxide previously stabilized with acetylacetone, and a solution in which the titania nanosheet produced in a) of Example 1 is dispersed (concentration of titania nanosheet 1% by weight) Each 5 ml was weighed, placed in a beaker and stirred for 30 minutes with a magnetic stirrer to prepare a coating solution. After that, the coating solution is applied on a pre-cleaned Pyrex (registered trademark) glass by a spin coating method (1000 rpm, 20 seconds), dried, and then baked at 450 ° C. for 3 hours to form a photocatalytic coating film. Formed.
(Comparative Example 2)
Commercially available high-temperature baking sol / gel type photocatalytic coating agent (Nippon Soda Co., Ltd.)
Vistraiter H Photocatalyst coating NDH-510C) is applied onto Pyrex (registered trademark) glass by spin coating (1000 rpm, 20 seconds), dried, and then baked at 450 ° C. for 3 hours to form a photocatalytic coating film did.
(Examination to confirm the effect)
(i) Visible light absorption characteristics The visible light absorption characteristics of the photocatalyst coating films produced in Example 1 and Comparative Example 1 were measured with an ultraviolet-visible spectrophotometer (manufactured by Hitachi High-Technologies Corporation: U-3310). The result is shown in FIG. As is clear from FIG. 2, the photocatalyst coating film produced in Example 1 has much higher absorption in the visible light region than the photocatalyst coating film produced in Comparative Example 1. This result confirms that the photocatalytic coating film produced in Example 1 has photocatalytic activity in the visible light region.
(ii) Hardness of the photocatalyst coating film The coating film hardness of the photocatalyst coating film produced in Example 1 and Comparative Example 2 was measured according to the pencil scratch test method in “JIS-K5400”. As a result, the coating film hardness of the photocatalyst coating film produced in Example 1 was 9H or higher, which was very high. On the other hand, the coating film hardness of the photocatalyst coating film produced in Comparative Example 2 was 6B.
(iii) Smoothness of coating film The surface of the photocatalyst coating film produced in Example 1 and Comparative Example 2 was measured using a scanning probe microscope (manufactured by JEOL Ltd .: JSPM-5200). The measurement conditions were tapping mode. The surface observation image of the photocatalyst coating film manufactured in Example 1 is shown in FIG. 3 (a), and the surface observation image of the photocatalyst coating film manufactured in Comparative Example 2 is shown in FIG. 3 (b). As apparent from FIG. 3A, the photocatalyst coating film produced in Example 1 was very dense and smooth, and the surface roughness Ra was 2.1 mm. On the other hand, as is clear from FIG. 3B, the surface of the photocatalyst coating film produced in Comparative Example 2 had large irregularities, and the surface roughness was 9.2 nm.
(iv) A methylene blue aqueous solution (concentration: 0.01 M), which is a model substance for antifouling soil, was prepared, and a glass piece on which a photocatalytic coating film was formed in Example 1 and a photocatalyst coating in Comparative Example 2 were prepared. Each piece of glass on which the film was formed was immersed for 12 hours. After the pulled glass piece was washed with water, the absorption spectrum of methylene blue adhering to the photocatalyst coating film was measured with an ultraviolet-visible spectrophotometer (manufactured by Hitachi High-Technologies Corporation: U-3310). The result is shown in FIG.
As is clear from FIG. 4, the photocatalyst coating film produced in Example 1 has a smaller absorption spectrum peak than the photocatalyst coating film produced in Comparative Example 2. From this, it can be seen that the photocatalyst coating film produced in Example 1 is a very dense and smooth coating film when fired, and that methylene blue hardly penetrates into and adheres to the inside of the coating film.
(v) Photo-induced hydrophilicity during irradiation with weak ultraviolet light Each of the photocatalyst coating films produced in Example 1 and Comparative Example 1 was irradiated with ultraviolet light for a predetermined time at an intensity of 5 μW / cm 2 close to the level of an indoor fluorescent lamp. Immediately thereafter, the contact angle of water was measured using a contact angle meter (manufactured by dataphysics: OCA15plus). The measurement was repeated while changing the irradiation time. The result is shown in FIG. As is clear from FIG. 5, the photocatalytic coating film produced in Example 1 became hydrophilic until the contact angle became 10 degrees or less after 10 minutes of irradiation, and the superhydrophilic state where the contact angle was 0 degrees after 20 minutes of irradiation. showed that. On the other hand, the photocatalytic coating film produced in Comparative Example 1 had a contact angle of 10 degrees or more even after 100 minutes of irradiation.
(vi) Light-induced hydrophilicity during visible light irradiation Next, based on the experimental method (v) above, the light source is a fluorescent lamp, and a filter that cuts a wavelength of 420 nm or less is attached to the light source. Went. The result is shown in FIG. As is clear from FIG. 6, the photocatalyst coating film produced in Example 1 became hydrophilic until the contact angle became around 10 degrees after 10 hours of irradiation, and the contact angle became 10 degrees or less after 35 hours of irradiation. On the other hand, the photocatalyst coating film produced in Comparative Example 1 had a contact angle of 45 degrees or more even after 35 hours of irradiation and was hardly hydrophilized.
尚、本発明は前記実施例になんら限定されるものではなく、本発明を逸脱しない範囲において種々の態様で実施しうることはいうまでもない。 Needless to say, the present invention is not limited to the above-described embodiments, and can be implemented in various modes without departing from the scope of the present invention.
１・・光触媒塗膜 ３・・・基板 ５・・・シート状酸化チタン
７・・・バインダー
1 .... Photocatalytic coating film 3 ... Substrate 5 ... Sheet titanium oxide 7 ... Binder
Claims (7)
含硫黄化合物と、
を含むコーティング剤。 Scaly titanium oxide particles,
A sulfur-containing compound;
Coating agent containing.
塗布された前記コーティング剤を乾燥させる乾燥工程と、を有することを特徴とする光触媒塗膜の形成方法。 An application step of applying the coating agent according to claim 1 or 2,
And a drying step of drying the applied coating agent.
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| JP2005126314A (en) * | 2003-09-29 | 2005-05-19 | Jfe Steel Kk | Method of manufacturing titanium oxide solution, titanium oxide solution and photocatalytic coating material |
| JP2005290369A (en) * | 2004-03-10 | 2005-10-20 | Central Japan Railway Co | Titanium oxide-coating agent, and forming method for titanium oxide-coating film |
| WO2006095464A1 (en) * | 2005-03-09 | 2006-09-14 | Central Japan Railway Company | Titanium oxide coating agent, and method for titanium oxide coating film formation |
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| JP2005126314A (en) * | 2003-09-29 | 2005-05-19 | Jfe Steel Kk | Method of manufacturing titanium oxide solution, titanium oxide solution and photocatalytic coating material |
| JP2005290369A (en) * | 2004-03-10 | 2005-10-20 | Central Japan Railway Co | Titanium oxide-coating agent, and forming method for titanium oxide-coating film |
| WO2006095464A1 (en) * | 2005-03-09 | 2006-09-14 | Central Japan Railway Company | Titanium oxide coating agent, and method for titanium oxide coating film formation |
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