JP4110799B2 - Photocatalyst paint and coating material having photocatalytic function obtained by applying the paint - Google Patents
Photocatalyst paint and coating material having photocatalytic function obtained by applying the paint Download PDFInfo
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- JP4110799B2 JP4110799B2 JP2002053408A JP2002053408A JP4110799B2 JP 4110799 B2 JP4110799 B2 JP 4110799B2 JP 2002053408 A JP2002053408 A JP 2002053408A JP 2002053408 A JP2002053408 A JP 2002053408A JP 4110799 B2 JP4110799 B2 JP 4110799B2
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- coating material
- photocatalyst
- titanium oxide
- oxide powder
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- 238000000576 coating method Methods 0.000 title claims description 80
- 239000011248 coating agent Substances 0.000 title claims description 77
- 239000000463 material Substances 0.000 title claims description 69
- 239000011941 photocatalyst Substances 0.000 title claims description 62
- 239000003973 paint Substances 0.000 title claims description 39
- 230000001699 photocatalysis Effects 0.000 title claims description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 59
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000011164 primary particle Substances 0.000 claims description 32
- 235000019441 ethanol Nutrition 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 26
- 239000007822 coupling agent Substances 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 18
- 239000011163 secondary particle Substances 0.000 claims description 12
- 230000005484 gravity Effects 0.000 claims description 10
- 239000004575 stone Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- -1 β-diketone Chemical compound 0.000 claims description 5
- 239000004568 cement Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000004567 concrete Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000123 paper Substances 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000010985 leather Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 22
- 239000010409 thin film Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 16
- 239000003960 organic solvent Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- 230000000844 anti-bacterial effect Effects 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003373 anti-fouling effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- GSOHKPVFCOWKPU-UHFFFAOYSA-N 3-methylpentane-2,4-dione Chemical compound CC(=O)C(C)C(C)=O GSOHKPVFCOWKPU-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BPIHCIRSGQKCLT-UHFFFAOYSA-N 3-propan-2-ylpentane-2,4-dione Chemical compound CC(C)C(C(C)=O)C(C)=O BPIHCIRSGQKCLT-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LCLCVVVHIPPHCG-UHFFFAOYSA-N 5,5-dimethylhexane-2,4-dione Chemical compound CC(=O)CC(=O)C(C)(C)C LCLCVVVHIPPHCG-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical group [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Chemical group 0.000 description 1
- 229910052760 oxygen Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、光触媒活性、透明性に優れた酸化チタン系光触媒塗料及びその製造方法並びに該塗料を塗布して得られた光触媒機能を有するコーティング材に関するものである。
【０００２】
【従来の技術】
この種の光触媒薄膜を得る方法として、特開平７−１００３７８号公報に記載されているように、チタンのアルコキシドとアルコールアミン類から調製されたチタニアゾルを基板にコーティングした後、焼成することにより光触媒薄膜を形成する方法が知られている。また、基板の保護及び酸化チタン層との密着性向上のために、基板と酸化チタン層との間にアンダーコート膜を設けた２層コートタイプの塗膜の製造方法も知られている。
【０００３】
このうち、チタニアゾルを用いて焼成する方法では、高温で焼成処理しなければならないため、得られた光触媒薄膜の透明性が低下するおそれがあるだけでなく、焼成炉を必要とするためコストが高くなる問題があった。
また、低温で処理できる２層コートタイプでは、２回塗り及び乾燥が必要であるため、処理工程が多くなり、簡便な方法とはいえなかった。この２層コートタイプでは光触媒の活性を十分に引き出すために、酸化チタンの含有量を８０重量％以上としなければならないため、成膜した膜の透明性が十分に得られないだけでなく、基板との密着性が十分に得られず安定した膜が形成できなくなるという問題があった。
【０００４】
上記諸問題を解決する方策として本出願人は、一次粒子の平均粒径０．０１〜０．１μｍの超微粒子アナターゼ型酸化チタン、有機溶媒、β-ジケトン、チタネート系又はアルミネート系カップリング剤とシリカゾルからなる光触媒塗料を提案した（特開平１０−１９５３４１号）。この公報に示された光触媒塗料を用いることにより、透明性、触媒活性、塗膜強度に優れた光触媒塗膜を形成することができる。
【０００５】
【発明が解決しようとする課題】
しかし、特開平１０−１９５３４１号公報に示された光触媒塗料を用いて塗膜を形成することにより、従来の光触媒薄膜と比べて高い透明性、光触媒活性、膜強度に優れた塗膜が得られるが、光触媒の用途の拡大とともに、より高い透明性を有する塗膜を形成し得る光触媒塗料の開発が要望されている。
【０００６】
本発明の目的は、透明性、硬度及び分解性能に優れた光触媒塗料及び該塗料を塗布して得られた光触媒機能を有するコーティング材を提供することにある。
【０００７】
【課題を解決するための手段】
請求項１に係る発明は、アナターゼ型酸化チタン粉末と混合アルコールとβ-ジケトンとチタネート系カップリング剤とシリカゾルを含む光触媒塗料の改良である。その特徴ある構成は、混合アルコールが４〜１５重量％のメチルアルコールと９６〜８５重量％のエチルアルコールの混合液であり、アナターゼ型酸化チタン粉末はその一次粒子径が０．０１〜０．０３μｍ及びその見掛比重が５０〜２００ｇ／Ｌであって、一次粒子及び一次粒子が凝集又は集塊した二次粒子からなる光触媒塗料である。
請求項１に係る発明では、このような物性を有するアナターゼ型酸化チタン粉末を塗料中に分散することにより、透明性、硬度及び分解性能に優れた光触媒塗料が得られる。
【０００８】
請求項２に係る発明は、請求項１に係る発明であって、アナターゼ型酸化チタン粉末はＢＥＴ比表面積が３０〜１００ｍ2／ｇであり、この一次粒子及び一次粒子が凝集又は集塊した二次粒子の粒子同士が０．０１〜０．３μｍの間隔をあけて塗料中に分散している光触媒塗料である。
請求項３に係る発明は、請求項１又は２に係る発明であって、酸化チタン粉末の含有量が０．５〜２０重量％である光触媒塗料である。
請求項４に係る発明は、請求項１ないし３いずれかに係る発明であって、β-ジケトンの含有量が酸化チタン粉末に対して０．５〜１０重量％である光触媒塗料である。
請求項５に係る発明は、請求項１ないし４いずれかに係る発明であって、チタネート系カップリング剤の添加量が酸化チタン粉末に対して０．１〜５重量％である光触媒塗料である。
請求項６に係る発明は、請求項１ないし５いずれかに係る発明であって、シリカゾルがエチルシリケートの加水分解物又は部分加水分解物である光触媒塗料である。
【０００９】
請求項２〜６に記載された構成にすることにより、より一層透明性、硬度及び分解性能に優れた光触媒塗料が得られる。
【００１１】
請求項７に係る発明は、請求項１ないし６いずれか記載の光触媒塗料を基材表面に塗布して形成させたことを特徴とする光触媒機能を有するコーティング材である。
請求項８に係る発明は、請求項７に係る発明であって、基材表面に無機質の下地層と、この下地層の上に光触媒塗料から形成された光触媒膜とを有するコーティング材である。
請求項９に係る発明は、請求項７又は８に係る発明であって、基材がガラス、プラスチック、金属、木材、タイルを含むセラミック、セメント、コンクリート、石、繊維、紙及び皮革からなる群より選ばれた材質であるコーティング材である。
請求項１０に係る発明は、請求項８に係る発明であって、無機質の下地層がシリカ又はアルミナからなるコーティング材である。
【００１２】
請求項１１に係る発明は、請求項７ないし１０いずれか記載のコーティング材により表面被覆を行った石材加工品である。
請求項１２に係る発明は、請求項７ないし１０いずれか記載のコーティング材により表面被覆を行った壁材である。
請求項１３に係る発明は、請求項７ないし１０いずれか記載のコーティング材により表面被覆を行った硝子である。
【００１３】
【発明の実施の形態】
次に本発明の実施の形態を説明する。
本発明者らは、その一次粒子径が０．０１〜０．０３μｍ及びその見掛比重が５０〜２００ｇ／Ｌであって、一次粒子及び一次粒子が凝集又は集塊した二次粒子からなることを特徴とするアナターゼ型酸化チタン粉末をβ-ジケトン、チタネート系カップリング剤存在下で、有機溶媒である混合アルコール中に均一に分散させた後、この分散液にシリカゾルを混合して得られる塗料は、より高い透明性を有し、硬度及び分解性能に優れた塗膜を形成することができるとの知見を得、本発明に至った。
【００１４】
一次粒子径が０．０１〜０．０３μｍ及び見掛比重が５０〜２００ｇ／Ｌの一次粒子及び一次粒子が凝集又は集塊した二次粒子からなるアナターゼ型酸化チタン粉末が、溶媒である混合アルコールとβ-ジケトンとチタネート系カップリング剤からなる液体中で、一次粒子に近い状態まで均一で高度に分散する。酸化チタン粉末は一次粒子径が０．０１μｍ未満のものは入手が困難であり、０．０３μｍを越えると光触媒塗料の透明度が低下する。見掛比重が５０ｇ／Ｌ未満であると均一に分散することができず、見掛比重が２００ｇ／Ｌを越えると塗膜の透明性において不具合を生じる。一次粒子と二次粒子の割合は個数比で一次粒子／二次粒子が１．０〜３．０であることが好ましい。一次粒子／二次粒子が下限値未満、即ち二次粒子が一次粒子に対して多くなると透明度が低下し易くなり、上限値を越えると製造が困難である。
【００１５】
この分散液に適量のシリカゾルを均一混合することにより、塗料中にアナターゼ型酸化チタン粉末が極めて一次粒子に近い状態まで均一で高度に分散した透明性、硬度及び分解性能に優れた光触媒塗料が得られる。
【００１６】
アナターゼ型酸化チタン粉末はそのＢＥＴ比表面積が３０〜１００ｍ2／ｇであることが好ましい。ＢＥＴ比表面積を３０〜１００ｍ2／ｇとしたのは、下限値未満では十分な触媒活性が得られず、上限値を越えると分散性が低下するからである。一次粒子及び一次粒子が凝集又は集塊した二次粒子の粒子同士は０．０１〜０．３μｍの間隔をあけて塗料中に分散させることが好ましい。このように酸化チタンの粒子同士が０．０１〜０．３μｍの間隔をあけることにより塗膜の透明度が低下しない。酸化チタンの粒子同士の間隔は０．０２〜０．１５μｍが好ましい。
この光触媒塗料を基材上に塗布することにより薄く均一な塗布が可能であり、かつβ-ジケトンとチタネート系カップリング剤更には、シリカゾルの作用により酸化チタン粒子間、及び基材との密着性が向上し、安定した光触媒薄膜が形成できる。
【００１７】
酸化チタン粉末の含有量は０．５〜２０重量％である。１．０〜１０．０重量％の割合で含有させることが好ましい。酸化チタン粉末の含有量が０．５重量％未満では十分な触媒活性が得られず、２０重量％を越えると酸化チタンの分散性が低下し、形成する光触媒薄膜のヘイズが悪化する不具合を生じる。
【００１８】
β-ジケトンは、極性官能基（ケトン基）が、酸化チタン微粉末及び基材表面に存在する極性基（水酸基や酸素基）に作用して、焼付け中に縮合することにより、酸化チタン粉末の最密充填が起こり、粉末間及び粉末-基板間を結合させ膜形成剤として作用し密着性を上げたのではないかと考えられる。
β-ジケトンとしては、２,４-ペンタンジオン、３-メチル-２,４-ペンタンジオン、３-イソプロピル-２,４-ペンタンジオン、２,２-ジメチル-３,５-ヘキサンジオン等が挙げられる。β-ジケトンは酸化チタン粉末に対して０．５〜１０重量％の割合で含有させる。１．０〜５．０重量％の割合で含有させることが好ましい。β-ジケトンの含有量が０．５重量％未満では、十分な分散性が得られず、１０．０重量％を越えても更なる分散性の向上にはならない。
【００１９】
カップリング剤は低ヘイズ化剤として作用する。カップリング剤を添加することにより、膜構造に二次凝集群を形成せず、均一な最密充填化と表面の平滑精度がより一層高められるためにヘイズが低下（透明性が向上する）すると推測される。
カップリング剤としては、下記式（１）〜式（５）に示されるようなジアルキルパイロホスフェート基やジアルキルホスファイト基を含有するチタネート系カップリング剤等が挙げられ、１種又は２種以上を使用することができる。
【００２０】
【化１】
【化２】
【化３】
【化４】
【化５】
チタネート系カップリング剤は酸化チタン粉末に対して０．１〜５重量％の割合で含有させる。０．５〜２．０重量％の割合で含有させることが好ましい。カップリング剤の含有量が０．１重量％未満では分散性及びヘイズ低下の効果が得られず、５．０重量％を越えても更なるヘイズ低下や分散性の向上にはならない。
【００２６】
溶媒として用いられる混合アルコールとしては、メチルアルコールとエチルアルコールからなる混合液が好適である。この混合アルコールの含有割合はメチルアルコールが４〜１５重量％、エチルアルコールが９６〜８５重量％である。メチルアルコールの含有割合が４重量％未満の場合、極めて透明な光触媒薄膜が得られず、１５重量％を越えても更なる効果は得られない。光触媒塗料に含まれる溶媒の量は、塗布に適した粘度が得られればよく、特に制限されない。
【００２７】
また、シリカゾルの均一混合作用により透明度を低下させることがなく、充分な触媒活性を得ることが出来、更にシリカゾルの作用で基材との密着性が一層向上する。
シリカゾルとしてはエチルシリケートの加水分解物又は部分加水分解物が挙げられる。
【００２８】
次に、光触媒塗料の製造方法について説明する。
先ずその一次粒子径が０．０１〜０．０３μｍ、その見掛比重が５０〜２００ｇ／Ｌ及びそのＢＥＴ比表面積が３０〜１００ｍ2／ｇの範囲内の物性を有し、一次粒子及び一次粒子が凝集又は集塊した二次粒子からなるアナターゼ型酸化チタン粉末を所定量用意する。このアナターゼ型酸化チタン粉末は四塩化チタンを高温気相中で加水分解反応させ、反応生成物を急速冷却することにより得られる。
次いでこの酸化チタン粉末を混合アルコールとβ-ジケトンとチタネート系カップリング剤からなる液体に混合し、例えばジルコニアビーズの所定量により、所定時間ペイントシェーカーにて均一に分散させる。次に、この分散液に所定濃度のシリカゾル溶液を適量加えて均一混合することにより、本発明の光触媒塗料を製造することができる。この光触媒塗料を例えばスピンコーターにより所定の基材表面に塗布し、乾燥することにより、その表面に光触媒塗膜を有するコーティング材が得られる。
【００２９】
また基材表面に無機質の下地層を形成し、この下地層の上に光触媒塗料を塗布、乾燥して光触媒膜を形成して光触媒機能を有するコーティング材を得ることもできる。本発明の光触媒塗料を用いた基材への塗布方法としては、スピンコート法、ディッピング法、スプレー法等により施すことができるが、特に塗布方法は限定されない。
【００３０】
本発明の基材に使用される材質には、ガラス、プラスチック、金属、木材、タイルを含むセラミック、セメント、コンクリート、石、繊維、紙及び皮革からなる群より選ばれる。ガラスとしては、蛍光灯、窓等の室内環境浄化（汚染物質分解）ガラス、水槽、生け簀等の水質浄化ガラス、車の防曇ガラス、ＣＲＴ、ＬＣＤ画面、窓、鏡、眼鏡等の防汚ガラス、カメラ、光学機器の防汚、防黴レンズ等がある。プラスチックとしては、ＡＶ機器、コンピューター、マウス、キーボード、リモコン、フロッピーディスク、等の機器及びその周辺製品、車の内装品、家具、キッチン、風呂、洗面所等で使用する家庭用品等の使用する防汚、抗菌、防黴プラスチック等がある。金属としては、物干し台、物干し竿、キッチン、実験室等の作業台や洗い場、換気扇等に使用する防汚、抗菌、防黴ステンレス、防汚、抗菌処理ドアノブ等がある。木材の用途としては、防汚家具、公園の抗菌遊技施設等がある。タイルを含むセラミック、セメント、コンクリート、石等の建材としては、防汚処理した外壁材、屋根、床材等、室内環境浄化（汚染物質分解）性を持つ内壁材、防汚、抗菌、防黴処理した各種内装品等がある。紙としては、抗菌処理文房具等に使用できる。フィルム等の繊維としては、食品包装用透明抗菌フィルム、野菜保存用透明エチレンガス分解フィルム、環境、水質浄化用フィルム等がある。このように各種基材は、防汚、環境浄化、抗菌、防黴の効果を有するので、太陽光や蛍光灯等から発せられる紫外線の照射が可能な条件であれば、例示した以外でも多くの用途に使用することができる。無機質の下地層としてはシリカ、アルミナ等が挙げられる。本発明のコーティング材により表面被覆を行った石材加工品、壁材又は硝子は透明性及び硬度に優れるとともに高い分解性能を示す。
【００３１】
【実施例】
次に本発明の実施例を比較例とともに詳しく説明する。
＜実施例１＞
有機溶媒に４．７重量％のメチルアルコールと９５．３重量％のエチルアルコールの混合アルコール４０ｇ、β-ジケトンに２,４-ペンタンジオン０．２５ｇ、上記化学式（１）に示されるチタネート系カップリング剤０．２５ｇ、一次粒子径０．０２１μｍ、見掛比重１３０ｇ／Ｌ、ＢＥＴ比表面積５０ｍ2／ｇのアナターゼ型酸化チタン１０ｇを混合し、ジリコニアビーズ１００ｇにより１６時間ペイントシェーカーにて分散させた。この分散液に１０重量％シリカゾル溶液１１ｇを混合し、光触媒塗料を調製した。調製した光触媒塗料をスピンコーターでガラス基板に塗布し、１２５℃で１時間乾燥させることにより、ガラス基板表面に光触媒薄膜が形成されたコーティング材を得た。得られた光触媒塗料の酸化チタン粉末の形態について透過型電子顕微鏡で測定したところ、粒子同士が０．０２〜０．３μｍの間隔をあけて塗料中に分散していることを確認した。
【００３２】
＜実施例２＞
有機溶媒に１０．２重量％のメチルアルコールと８９．８重量％のエチルアルコールの混合アルコール１５０ｇ、上記化学式（１）に示されるチタネート系カップリング剤０．１ｇを用いた以外は実施例１と同様にして光触媒塗料を調製し、実施例１と同様の方法でガラス基板表面に光触媒薄膜を形成した。得られた光触媒塗料の酸化チタン粉末の形態について透過型電子顕微鏡で測定したところ、粒子同士が０．０１〜０．１５μｍの間隔をあけて塗料中に分散していることを確認した。
＜実施例３＞
有機溶媒に４．７重量％のメチルアルコールと９５．３重量％のエチルアルコールの混合アルコール１５０ｇ、上記化学式（２）に示されるチタネート系カップリング剤０．１ｇを用いた以外は実施例１と同様にして光触媒塗料を調製し、実施例１と同様の方法でガラス基板表面に光触媒薄膜を形成した。得られた光触媒塗料の酸化チタン粉末の形態について透過型電子顕微鏡で測定したところ、粒子同士が０．０２〜０．１５μｍの間隔をあけて塗料中に分散していることを確認した。
＜実施例４＞
有機溶媒に１０．２重量％のメチルアルコールと８９．８重量％のエチルアルコールの混合アルコール４０ｇ、β-ジケトンに３-メチル-２,４-ペンタンジオン０．５ｇ、上記化学式（３）に示されるチタネート系カップリング剤０．５ｇを用いた以外は実施例１と同様にして光触媒塗料を調製し、実施例１と同様の方法でガラス基板表面に光触媒薄膜を形成した。得られた光触媒塗料の酸化チタン粉末の形態について透過型電子顕微鏡で測定したところ、粒子同士が０．０５〜０．２０μｍの間隔をあけて塗料中に分散していることを確認した。
【００３３】
＜実施例５＞
有機溶媒に１０．２重量％のメチルアルコールと８９．８重量％のエチルアルコールの混合アルコール１５０ｇ、β-ジケトンに３-メチル-２,４-ペンタンジオン０．５ｇ、上記化学式（４）に示されるチタネート系カップリング剤０．２５ｇ、１０重量％シリカゾル溶液４３ｇを用いた以外は実施例１と同様にして光触媒塗料を調製し、実施例１と同様の方法でガラス基板表面に光触媒薄膜を形成した。得られた光触媒塗料の酸化チタン粉末の形態について透過型電子顕微鏡で測定したところ、粒子同士が０．０５〜０．１０μｍの間隔をあけて塗料中に分散していることを確認した。
＜実施例６＞
有機溶媒に４．７重量％のメチルアルコールと９５．３重量％のエチルアルコールの混合アルコール４０ｇ、β-ジケトンに３-イソプロピル-２,４-ペンタンジオン１．０ｇ、上記化学式（５）に示されるチタネート系カップリング剤０．４ｇ、１０重量％シリカゾル溶液４３ｇを用いた以外は実施例１と同様にして光触媒塗料を調製し、実施例１と同様の方法でガラス基板表面に光触媒薄膜を形成した。得られた光触媒塗料の酸化チタン粉末の形態について透過型電子顕微鏡で測定したところ、粒子同士が０．０５〜０．２５μｍの間隔をあけて塗料中に分散していることを確認した。
【００３４】
＜比較例１＞
有機溶媒にエチルアルコール４０ｇ、上記化学式（１）に示されるチタネート系カップリング剤０．１ｇを用いた以外は実施例１と同様にして光触媒塗料を調製し、実施例１と同様の方法でガラス基板表面に光触媒薄膜を形成した。得られた光触媒塗料の酸化チタン粉末の形態について透過型電子顕微鏡で測定したところ、粒子同士が０．１〜０．４μｍの間隔をあけて塗料中に分散していることを確認した。
＜比較例２＞
有機溶媒にエチルアルコール４０ｇ、上記化学式（２）に示されるチタネート系カップリング剤０．４ｇを用い、β-ジケトンを添加しない以外は実施例１と同様にして光触媒塗料を調製し、実施例１と同様の方法でガラス基板表面に光触媒薄膜を形成した。得られた光触媒塗料の酸化チタン粉末の形態について透過型電子顕微鏡で測定したところ、粒子同士が０．２〜０．５μｍの間隔をあけて塗料中に分散していることを確認した。
【００３５】
＜比較例３＞
有機溶媒にエチルアルコール４０ｇ、β-ジケトンに２,４-ペンタンジオン０．５ｇ、１０重量％シリカゾル溶液４３ｇを用い、チタネートカップリング剤を添加しない以外は実施例１と同様にして光触媒塗料を調製し、実施例１と同様の方法でガラス基板表面に光触媒薄膜を形成した。得られた光触媒塗料の酸化チタン粉末の形態について透過型電子顕微鏡で測定したところ、粒子同士が０．２〜０．５μｍの間隔をあけて塗料中に分散していることを確認した。
＜比較例４＞
酸化チタンに一次粒子径０．０４μｍ、見掛比重２５０ｇ／Ｌ、ＢＥＴ比表面積２５ｍ2／ｇのアナターゼ型酸化チタン１０ｇを用いた以外は実施例１と同様にして光触媒塗料を調製し、実施例１と同様の方法でガラス基板表面に光触媒薄膜を形成した。得られた光触媒塗料の酸化チタン粉末の形態について透過型電子顕微鏡で測定したところ、粒子同士が０．２〜０．４μｍの間隔をあけて塗料中に分散していることを確認した。
【００３６】
＜比較試験及び評価＞
実施例１〜６及び比較例１〜４で得られたコーティング材の光触媒薄膜について光触媒薄膜のヘイズ、鉛筆硬度及び光触媒活性をそれぞれ測定した。なお、ヘイズ測定には、スガ試験機社製ヘイズコンピューターＨＧＭ−３Ｄを用いた。また光触媒活性は、以下に示す手順により求めた除去率を光触媒活性の指標とした。先ず、光触媒薄膜を塗布したガラス基板を１Ｌのガラス（パイレックス）製容器に入れて密閉した。次いで容器内に３５０ｐｐｍ（初期濃度）のアセトアルデヒドを導入した。次に、容器を照射量１．２ｍＷ／ｃｍ2の紫外線ランプで２時間照射した。照射後の容器内部のアセトアルデヒド濃度をガス検知管（ガステック社製）で測定し、下記に示す式に基づいて除去率を求めた。
【００３７】
除去率[％]＝[(初期濃度−光照射後の濃度)÷初期濃度]×１００
実施例１〜６及び比較例１〜４で得られたコーティング材の光触媒薄膜について測定した結果を表１にそれぞれ示す。
【００３８】
【表１】
表１より明らかなように、有機溶媒にエチルアルコールを用いた比較例１〜３では、ヘイズが高く透明性に劣り、鉛筆による硬度でもＨ〜３Ｈと柔らかく、アセトアルデヒド除去率も７５〜９０％と低い数値を示している。また物性が本発明の範囲外である酸化チタンを用いた比較例４でも、ヘイズ値が高く、鉛筆硬度、アセトアルデヒド除去率ともに低くなった。これに対して実施例１〜６ではヘイズが極めて低く、鉛筆による硬度も３Ｈ〜４Ｈと硬く、アセトアルデヒド除去率は８５〜９５％と高い除去率を示した。
【００４０】
【発明の効果】
以上述べたように、本発明によれば、その一次粒子径が０．０１〜０．０３μｍ及びその見掛比重が５０〜２００ｇ／Ｌであって、一次粒子及び一次粒子が凝集又は集塊した二次粒子からなるアナターゼ型酸化チタン粉末をβ-ジケトンとチタネート系カップリング剤の存在下で溶媒である４〜１５重量％のメチルアルコールと９６〜８５重量％のエチルアルコールからなる混合アルコール中に均一に分散させた後、シリカゾルを混合することにより、アナターゼ型酸化チタン粉末が極めて一次粒子に近い状態まで均一で高度に分散した透明性、硬度及び分解性能に優れた光触媒塗料が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a titanium oxide photocatalyst paint excellent in photocatalytic activity and transparency, a method for producing the same, and a coating material having a photocatalytic function obtained by applying the paint.
[0002]
[Prior art]
As a method for obtaining this type of photocatalyst thin film, as described in JP-A-7-1000037, a titania sol prepared from an alkoxide of titanium and an alcoholamine is coated on a substrate and then fired to form a photocatalytic thin film. A method of forming is known. Also known is a method for producing a two-layer coat type coating film in which an undercoat film is provided between a substrate and a titanium oxide layer in order to protect the substrate and improve adhesion to the titanium oxide layer.
[0003]
Of these, the method of firing using titania sol requires firing at a high temperature, which not only reduces the transparency of the resulting photocatalyst thin film, but also requires a firing furnace, resulting in high costs. There was a problem.
In addition, the two-layer coating type that can be processed at a low temperature requires two coatings and drying, so that the number of processing steps is increased, which is not a simple method. In this two-layer coating type, the titanium oxide content must be 80% by weight or more in order to sufficiently bring out the activity of the photocatalyst. There was a problem that a sufficient film could not be formed and a stable film could not be formed.
[0004]
As a measure for solving the above-mentioned problems, the present applicant has proposed an ultrafine particulate anatase-type titanium oxide having an average primary particle size of 0.01 to 0.1 μm, an organic solvent, a β-diketone, a titanate-based or aluminate-based coupling agent. And a photocatalytic coating material composed of silica sol was proposed (Japanese Patent Laid-Open No. 10-195341). By using the photocatalyst paint disclosed in this publication, a photocatalyst coating film excellent in transparency, catalytic activity, and coating film strength can be formed.
[0005]
[Problems to be solved by the invention]
However, by forming a coating film using the photocatalyst paint disclosed in JP-A-10-195341, a coating film having higher transparency, photocatalytic activity, and film strength than a conventional photocatalyst thin film can be obtained. However, development of a photocatalyst coating capable of forming a coating film having higher transparency is demanded as the use of the photocatalyst is expanded.
[0006]
An object of the present invention is to provide a transparent coating material having a photocatalytic function obtained by applying a hardness and decomposition performance excellent in the photocatalytic coating及beauty the paint.
[0007]
[Means for Solving the Problems]
The invention according to claim 1 is an improvement of a photocatalytic coating material comprising anatase-type titanium oxide powder, mixed alcohol, β-diketone, titanate coupling agent, and silica sol. The characteristic structure is a mixed solution of 4 to 15% by weight of methyl alcohol and 96 to 85% by weight of ethyl alcohol. The anatase-type titanium oxide powder has a primary particle size of 0.01 to 0.03 μm. And the apparent specific gravity is 50-200 g / L, Comprising: It is a photocatalyst coating material which consists of a secondary particle which the primary particle and the primary particle aggregated or agglomerated.
In the invention which concerns on Claim 1, the photocatalyst coating material excellent in transparency, hardness, and decomposition | disassembly performance is obtained by disperse | distributing the anatase type titanium oxide powder which has such a physical property in a coating material.
[0008]
The invention according to claim 2 is the invention according to claim 1, wherein the anatase-type titanium oxide powder has a BET specific surface area of 30 to 100 m 2 / g, and the primary particles and the primary particles are aggregated or agglomerated. This is a photocatalytic coating in which the particles of the next particles are dispersed in the coating at an interval of 0.01 to 0.3 μm.
The invention according to claim 3 is the invention according to claim 1 or 2, wherein the content of the titanium oxide powder is 0.5 to 20% by weight.
The invention according to claim 4 is the photocatalyst paint according to any one of claims 1 to 3, wherein the content of β-diketone is 0.5 to 10% by weight based on the titanium oxide powder.
The invention according to claim 5 is the photocatalyst paint according to any one of claims 1 to 4, wherein the titanate coupling agent is added in an amount of 0.1 to 5% by weight based on the titanium oxide powder. .
The invention according to claim 6 is the photocatalyst coating material according to any one of claims 1 to 5 , wherein the silica sol is a hydrolyzate or a partial hydrolyzate of ethyl silicate.
[0009]
By adopting the constitution described in claims 2 to 6 , a photocatalyst coating material that is further excellent in transparency, hardness, and decomposition performance can be obtained.
[0011]
The invention according to claim 7 is a coating material having a photocatalytic function, characterized in that the claims 1 to photocatalytic paint 6 wherein any one was formed by coating on the substrate surface.
The invention according to claim 8 is the invention according to claim 7 , which is a coating material having an inorganic underlayer on the surface of a substrate and a photocatalyst film formed from a photocatalyst paint on the underlayer.
The invention according to claim 9 is the invention according to claim 7 or 8 , wherein the substrate is made of glass, plastic, metal, wood, tile-containing ceramic, cement, concrete, stone, fiber, paper and leather. It is a coating material that is a more selected material.
The invention according to claim 10 is the invention according to claim 8 , wherein the inorganic underlayer is a coating material made of silica or alumina.
[0012]
The invention according to an eleventh aspect is a processed stone material that is surface-coated with the coating material according to any one of the seventh to tenth aspects.
The invention according to claim 12 is a wall material that is surface-coated with the coating material according to any one of claims 7 to 10 .
A thirteenth aspect of the invention is a glass surface-coated with the coating material according to any one of the seventh to tenth aspects.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Next, an embodiment of the present invention will be described.
The inventors have a primary particle diameter of 0.01 to 0.03 μm, an apparent specific gravity of 50 to 200 g / L, and primary particles and secondary particles that are aggregated or agglomerated. A paint obtained by uniformly dispersing anatase-type titanium oxide powder characterized by the above in a mixed alcohol as an organic solvent in the presence of a β-diketone and a titanate coupling agent, and then mixing silica sol with this dispersion Has obtained the knowledge that a coating film having higher transparency and excellent hardness and decomposition performance can be formed, leading to the present invention.
[0014]
Mixed alcohol in which anatase-type titanium oxide powder comprising primary particles having a primary particle diameter of 0.01 to 0.03 μm and an apparent specific gravity of 50 to 200 g / L and secondary particles in which primary particles are aggregated or agglomerated is a solvent In a liquid consisting of, β-diketone and titanate coupling agent, it is uniformly and highly dispersed to a state close to primary particles. Titanium oxide powder having a primary particle size of less than 0.01 μm is difficult to obtain, and if it exceeds 0.03 μm, the transparency of the photocatalyst coating material is lowered. If the apparent specific gravity is less than 50 g / L, it cannot be uniformly dispersed, and if the apparent specific gravity exceeds 200 g / L, a defect occurs in the transparency of the coating film. The ratio of primary particles to secondary particles is preferably 1.0 to 3.0 in terms of the number ratio of primary particles / secondary particles. When the primary particle / secondary particle is less than the lower limit, that is, when the secondary particle is larger than the primary particle, the transparency tends to be lowered, and when the upper limit is exceeded, the production is difficult.
[0015]
By uniformly mixing an appropriate amount of silica sol with this dispersion, a photocatalyst coating with excellent transparency, hardness and decomposition performance is obtained in which the anatase-type titanium oxide powder is uniformly and highly dispersed in the coating to a state close to primary particles. It is done.
[0016]
The anatase-type titanium oxide powder preferably has a BET specific surface area of 30 to 100 m 2 / g. The reason why the BET specific surface area is set to 30 to 100 m 2 / g is that sufficient catalytic activity cannot be obtained if it is less than the lower limit value, and dispersibility is lowered if the upper limit value is exceeded. It is preferable to disperse | distribute the primary particle and the particle | grains of the secondary particle which the primary particle aggregated or agglomerated in the coating material at intervals of 0.01-0.3 micrometer. Thus, the transparency of a coating film does not fall because the particle | grains of titanium oxide leave a space | interval of 0.01-0.3 micrometer. The distance between the titanium oxide particles is preferably 0.02 to 0.15 μm.
By applying this photocatalyst paint on the substrate, thin and uniform coating is possible, and β-diketone, titanate coupling agent, and the adhesion between titanium oxide particles and the substrate by the action of silica sol. And a stable photocatalytic thin film can be formed.
[0017]
The content of titanium oxide powder is 0.5 to 20% by weight. It is preferable to make it contain in the ratio of 1.0-10.0 weight%. When the content of the titanium oxide powder is less than 0.5% by weight, sufficient catalytic activity cannot be obtained. When the content exceeds 20% by weight, the dispersibility of the titanium oxide is lowered, and the haze of the formed photocatalytic thin film is deteriorated. .
[0018]
In β-diketone, the polar functional group (ketone group) acts on the titanium oxide fine powder and the polar group (hydroxyl group and oxygen group) present on the surface of the base material and condenses during baking, so that the titanium oxide powder It is thought that close packing occurred and the adhesion between the powder and the powder-substrate was increased by acting as a film forming agent.
Examples of β-diketones include 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-isopropyl-2,4-pentanedione, 2,2-dimethyl-3,5-hexanedione, and the like. It is done. β-diketone is contained in a proportion of 0.5 to 10% by weight based on the titanium oxide powder. It is preferable to make it contain in the ratio of 1.0-5.0 weight%. If the content of β-diketone is less than 0.5% by weight, sufficient dispersibility cannot be obtained, and if it exceeds 10.0% by weight, no further improvement in dispersibility is obtained.
[0019]
The coupling agent acts as a low haze agent. By adding a coupling agent, the secondary aggregate group is not formed in the film structure, and the haze is lowered (transparency is improved) because uniform close-packing and surface smoothness accuracy are further enhanced. Guessed.
Examples of the coupling agent include titanate coupling agents containing a dialkyl pyrophosphate group or a dialkyl phosphite group as shown in the following formulas (1) to (5). Can be used.
[0020]
[Chemical 1]
[Chemical formula 2]
[Chemical 3]
[Formula 4]
[Chemical formula 5]
The titanate coupling agent is contained in a proportion of 0.1 to 5% by weight with respect to the titanium oxide powder. It is preferable to make it contain in the ratio of 0.5 to 2.0 weight%. If the content of the coupling agent is less than 0.1% by weight, the effects of dispersibility and haze reduction cannot be obtained, and if it exceeds 5.0% by weight, further haze reduction and dispersibility cannot be improved.
[0026]
As the mixed alcohol used as the solvent, a mixed liquid composed of methyl alcohol and ethyl alcohol is suitable. The content ratio of the mixed alcohol is 4 to 15% by weight of methyl alcohol and 96 to 85% by weight of ethyl alcohol. When the content ratio of methyl alcohol is less than 4% by weight, a very transparent photocatalytic thin film cannot be obtained, and even if the content exceeds 15% by weight, no further effect can be obtained. The amount of the solvent contained in the photocatalyst coating is not particularly limited as long as a viscosity suitable for application can be obtained.
[0027]
Further, the transparency of the silica sol is not lowered by the uniform mixing action of the silica sol, and sufficient catalytic activity can be obtained. Further, the adhesion to the substrate is further improved by the action of the silica sol.
Examples of the silica sol include a hydrolyzate or partial hydrolyzate of ethyl silicate.
[0028]
Next, the manufacturing method of a photocatalyst coating material is demonstrated.
First, the primary particle diameter is 0.01 to 0.03 μm, the apparent specific gravity is 50 to 200 g / L, and the BET specific surface area is in the range of 30 to 100 m 2 / g. A predetermined amount of anatase-type titanium oxide powder consisting of secondary particles that are aggregated or agglomerated is prepared. This anatase-type titanium oxide powder is obtained by hydrolyzing titanium tetrachloride in a high-temperature gas phase and rapidly cooling the reaction product.
Next, the titanium oxide powder is mixed with a liquid composed of a mixed alcohol, β-diketone, and titanate coupling agent, and is uniformly dispersed in a paint shaker for a predetermined time with a predetermined amount of zirconia beads, for example. Next, the photocatalyst coating material of the present invention can be produced by adding an appropriate amount of a silica sol solution having a predetermined concentration to this dispersion and mixing them uniformly. The photocatalyst paint is applied to the surface of a predetermined substrate by, for example, a spin coater and dried to obtain a coating material having a photocatalyst coating film on the surface.
[0029]
It is also possible to obtain a coating material having a photocatalytic function by forming an inorganic underlayer on the surface of the substrate and applying a photocatalyst coating on the underlayer and drying to form a photocatalyst film. As a coating method to the base material using the photocatalyst coating material of the present invention, it can be applied by spin coating method, dipping method, spraying method or the like, but the coating method is not particularly limited.
[0030]
The material used for the substrate of the present invention is selected from the group consisting of glass, plastic, metal, wood, ceramic including tile, cement, concrete, stone, fiber, paper, and leather. Glasses include fluorescent lamps, windows and other indoor environment purification (pollutant decomposition) glass, water tanks, water purification glass such as sacrifices, car anti-fog glass, CRT, LCD screens, windows, mirrors, glasses, etc. , Anti-fouling, anti-fouling lenses, etc. for cameras and optical equipment. Plastics include AV equipment, computers, mice, keyboards, remote controls, floppy disks, etc. and peripheral products, car interiors, furniture, kitchens, bathrooms, household items used in bathrooms, etc. There are dirt, antibacterial, anti-bacterial plastic and so on. Examples of the metal include clothes racks, clothes racks, kitchen benches, laboratory benches and antifouling, antibacterial, antibacterial stainless steel, antifouling and antibacterial door knobs used for ventilation fans. Wood applications include antifouling furniture and park antibacterial amusement facilities. As building materials such as ceramics, cement, concrete and stone including tiles, anti-stain-treated outer wall materials, roofs, floor materials, etc., interior wall materials with indoor environment purification (contaminant decomposition), anti-fouling, antibacterial, anti-fouling There are various interior items that have been processed. As paper, it can be used for antibacterial treatment stationery and the like. Examples of the fiber such as a film include a transparent antibacterial film for food packaging, a transparent ethylene gas decomposition film for preservation of vegetables, a film for environmental and water purification, and the like. As described above, since various base materials have antifouling, environmental purification, antibacterial, and antifungal effects, there are many other than those exemplified as long as they can be irradiated with ultraviolet rays emitted from sunlight or fluorescent lamps. Can be used for applications. Examples of the inorganic underlayer include silica and alumina. A processed stone material, wall material or glass which has been surface-coated with the coating material of the present invention is excellent in transparency and hardness and exhibits high decomposition performance.
[0031]
【Example】
Next, examples of the present invention will be described in detail together with comparative examples.
<Example 1>
40 g of mixed alcohol of 4.7% by weight methyl alcohol and 95.3% by weight ethyl alcohol in organic solvent, 0.25 g of 2,4-pentanedione in β-diketone, titanate cup represented by the above chemical formula (1) 10 g of anatase-type titanium oxide having a ring agent of 0.25 g, a primary particle diameter of 0.021 μm, an apparent specific gravity of 130 g / L, and a BET specific surface area of 50 m 2 / g are mixed and dispersed with 100 g of zirconia beads in a paint shaker for 16 hours. It was. 11 g of a 10 wt% silica sol solution was mixed with this dispersion to prepare a photocatalyst paint. The prepared photocatalyst coating material was applied to a glass substrate with a spin coater and dried at 125 ° C. for 1 hour to obtain a coating material in which a photocatalytic thin film was formed on the glass substrate surface. When the form of the titanium oxide powder of the obtained photocatalyst paint was measured with a transmission electron microscope, it was confirmed that the particles were dispersed in the paint with an interval of 0.02 to 0.3 μm.
[0032]
<Example 2>
Example 1 except that 150 g of a mixed alcohol of 10.2 wt% methyl alcohol and 89.8 wt% ethyl alcohol and 0.1 g of a titanate coupling agent represented by the above chemical formula (1) were used as the organic solvent. Similarly, a photocatalyst paint was prepared, and a photocatalyst thin film was formed on the glass substrate surface in the same manner as in Example 1. When the form of the titanium oxide powder of the obtained photocatalyst paint was measured with a transmission electron microscope, it was confirmed that the particles were dispersed in the paint with an interval of 0.01 to 0.15 μm.
<Example 3>
Example 1 except that 150 g of a mixed alcohol of 4.7% by weight methyl alcohol and 95.3% by weight ethyl alcohol and 0.1 g of the titanate coupling agent represented by the above chemical formula (2) were used as the organic solvent. Similarly, a photocatalyst paint was prepared, and a photocatalyst thin film was formed on the glass substrate surface in the same manner as in Example 1. When the form of the titanium oxide powder of the obtained photocatalyst coating material was measured with a transmission electron microscope, it was confirmed that the particles were dispersed in the coating material with an interval of 0.02 to 0.15 μm.
<Example 4>
40g of mixed alcohol of 10.2% by weight methyl alcohol and 89.8% by weight ethyl alcohol in organic solvent, 0.5g of 3-methyl-2,4-pentanedione in β-diketone, shown in the above chemical formula (3) A photocatalyst paint was prepared in the same manner as in Example 1 except that 0.5 g of the titanate coupling agent was used, and a photocatalytic thin film was formed on the glass substrate surface in the same manner as in Example 1. When the form of the titanium oxide powder of the obtained photocatalyst coating material was measured with a transmission electron microscope, it was confirmed that the particles were dispersed in the coating material with an interval of 0.05 to 0.20 μm.
[0033]
<Example 5>
150 g of mixed alcohol of 10.2 wt% methyl alcohol and 89.8 wt% ethyl alcohol in organic solvent, 0.5 g of 3-methyl-2,4-pentanedione in β-diketone, as shown in the above chemical formula (4) A photocatalyst paint was prepared in the same manner as in Example 1 except that 0.25 g of titanate coupling agent and 43 g of 10 wt% silica sol solution were used, and a photocatalytic thin film was formed on the glass substrate surface in the same manner as in Example did. When the form of the titanium oxide powder of the obtained photocatalyst coating material was measured with a transmission electron microscope, it was confirmed that the particles were dispersed in the coating material with an interval of 0.05 to 0.10 μm.
<Example 6>
40 g of mixed alcohol of 4.7% by weight methyl alcohol and 95.3% by weight ethyl alcohol in an organic solvent, 1.0 g of 3-isopropyl-2,4-pentanedione in β-diketone, as shown in the above chemical formula (5) A photocatalyst paint was prepared in the same manner as in Example 1 except that 0.4 g of titanate coupling agent and 43 g of 10 wt% silica sol solution were used, and a photocatalytic thin film was formed on the glass substrate surface in the same manner as in Example 1. did. When the form of the titanium oxide powder of the obtained photocatalyst coating material was measured with a transmission electron microscope, it was confirmed that the particles were dispersed in the coating material with an interval of 0.05 to 0.25 μm.
[0034]
<Comparative Example 1>
A photocatalyst paint was prepared in the same manner as in Example 1 except that 40 g of ethyl alcohol and 0.1 g of the titanate coupling agent represented by the above chemical formula (1) were used as the organic solvent. A photocatalytic thin film was formed on the substrate surface. When the form of the titanium oxide powder of the obtained photocatalyst paint was measured with a transmission electron microscope, it was confirmed that the particles were dispersed in the paint with an interval of 0.1 to 0.4 μm.
<Comparative example 2>
A photocatalyst paint was prepared in the same manner as in Example 1 except that 40 g of ethyl alcohol and 0.4 g of the titanate coupling agent represented by the above chemical formula (2) were used as the organic solvent, and no β-diketone was added. A photocatalytic thin film was formed on the surface of the glass substrate by the same method. When the form of the titanium oxide powder of the obtained photocatalyst paint was measured with a transmission electron microscope, it was confirmed that the particles were dispersed in the paint with an interval of 0.2 to 0.5 μm.
[0035]
<Comparative Example 3>
A photocatalyst paint was prepared in the same manner as in Example 1 except that 40 g of ethyl alcohol was used as the organic solvent, 0.5 g of 2,4-pentanedione was used as the β-diketone, and 43 g of a 10 wt% silica sol solution was added, and no titanate coupling agent was added. Then, a photocatalytic thin film was formed on the surface of the glass substrate by the same method as in Example 1. When the form of the titanium oxide powder of the obtained photocatalyst paint was measured with a transmission electron microscope, it was confirmed that the particles were dispersed in the paint with an interval of 0.2 to 0.5 μm.
<Comparative example 4>
A photocatalytic coating was prepared in the same manner as in Example 1 except that 10 g of anatase-type titanium oxide having a primary particle size of 0.04 μm, an apparent specific gravity of 250 g / L, and a BET specific surface area of 25 m 2 / g was used as titanium oxide. 1 was used to form a photocatalytic thin film on the surface of the glass substrate. When the form of the titanium oxide powder of the obtained photocatalyst paint was measured with a transmission electron microscope, it was confirmed that the particles were dispersed in the paint with an interval of 0.2 to 0.4 μm.
[0036]
<Comparison test and evaluation>
About the photocatalyst thin film of the coating material obtained in Examples 1-6 and Comparative Examples 1-4, the haze, pencil hardness, and photocatalytic activity of the photocatalyst thin film were measured, respectively. For haze measurement, a haze computer HGM-3D manufactured by Suga Test Instruments Co., Ltd. was used. In addition, the photocatalytic activity was determined using the removal rate obtained by the following procedure as an index of photocatalytic activity. First, the glass substrate coated with the photocatalytic thin film was placed in a 1 L glass (pyrex) container and sealed. Next, 350 ppm (initial concentration) of acetaldehyde was introduced into the container. Next, the container was irradiated with an ultraviolet lamp having an irradiation amount of 1.2 mW / cm 2 for 2 hours. The acetaldehyde concentration inside the container after irradiation was measured with a gas detector tube (manufactured by Gastec Corporation), and the removal rate was determined based on the formula shown below.
[0037]
Removal rate [%] = [(initial density−density after light irradiation) ÷ initial density] × 100
Table 1 shows the measurement results of the photocatalytic thin films of the coating materials obtained in Examples 1 to 6 and Comparative Examples 1 to 4.
[0038]
[Table 1]
As is clear from Table 1, in Comparative Examples 1 to 3 using ethyl alcohol as the organic solvent, the haze is high and the transparency is poor, the hardness with a pencil is as soft as H to 3H, and the acetaldehyde removal rate is 75 to 90%. It shows a low number. Moreover, also in Comparative Example 4 using titanium oxide whose physical properties were outside the scope of the present invention, the haze value was high, and both the pencil hardness and the acetaldehyde removal rate were low. On the other hand, in Examples 1-6, the haze was extremely low, the hardness by pencil was as hard as 3H-4H, and the acetaldehyde removal rate was as high as 85-95%.
[0040]
【The invention's effect】
As described above, according to the present invention, the primary particle diameter is 0.01 to 0.03 μm and the apparent specific gravity is 50 to 200 g / L, and the primary particles and the primary particles are aggregated or agglomerated. the anatase type titanium oxide powder comprising secondary particles β- diketone and a mixed alcohol comprising a 4-15 wt% of methyl alcohol and 96 to 85 wt% of ethyl alcohol as a solvent in the presence of a titanate coupling agent After uniformly dispersing, the silica sol is mixed to obtain a photocatalyst coating material excellent in transparency, hardness and decomposition performance in which the anatase-type titanium oxide powder is uniformly and highly dispersed to a state close to primary particles.
Claims (13)
前記混合アルコールが４〜１５重量％のメチルアルコールと９６〜８５重量％のエチルアルコールの混合液であり、
前記アナターゼ型酸化チタン粉末はその一次粒子径が０．０１〜０．０３μｍ及びその見掛比重が５０〜２００ｇ／Ｌであって、前記一次粒子及び前記一次粒子が凝集又は集塊した二次粒子からなることを特徴とする光触媒塗料。In photocatalyst paint containing anatase type titanium oxide powder, mixed alcohol, β-diketone, titanate coupling agent and silica sol,
The mixed alcohol is a mixed solution of 4 to 15% by weight of methyl alcohol and 96 to 85% by weight of ethyl alcohol;
The anatase-type titanium oxide powder has a primary particle diameter of 0.01 to 0.03 μm and an apparent specific gravity of 50 to 200 g / L, and the primary particles and the primary particles are agglomerated or agglomerated secondary particles. A photocatalytic coating material comprising:
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