JP4738736B2 - Photocatalyst composite, coating solution for forming photocatalyst layer, and photocatalyst carrying structure - Google Patents
Photocatalyst composite, coating solution for forming photocatalyst layer, and photocatalyst carrying structure Download PDFInfo
- Publication number
- JP4738736B2 JP4738736B2 JP2003535930A JP2003535930A JP4738736B2 JP 4738736 B2 JP4738736 B2 JP 4738736B2 JP 2003535930 A JP2003535930 A JP 2003535930A JP 2003535930 A JP2003535930 A JP 2003535930A JP 4738736 B2 JP4738736 B2 JP 4738736B2
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- JP
- Japan
- Prior art keywords
- photocatalyst
- colloidal silica
- silica particles
- forming
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000011941 photocatalyst Substances 0.000 title claims description 215
- 239000011248 coating agent Substances 0.000 title claims description 63
- 238000000576 coating method Methods 0.000 title claims description 63
- 239000002131 composite material Substances 0.000 title claims description 10
- -1 aluminum compound Chemical class 0.000 claims description 103
- 239000002245 particle Substances 0.000 claims description 103
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 96
- 239000010410 layer Substances 0.000 claims description 94
- 239000008119 colloidal silica Substances 0.000 claims description 88
- 239000012790 adhesive layer Substances 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 42
- 229910052782 aluminium Inorganic materials 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 150000003755 zirconium compounds Chemical class 0.000 claims description 27
- 229920001296 polysiloxane Polymers 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 150000004703 alkoxides Chemical class 0.000 claims description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 238000011156 evaluation Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
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- 150000003377 silicon compounds Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
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- 238000012360 testing method Methods 0.000 description 25
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
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- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
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- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- B01J35/39—
Description
技術分野：
本発明は、浄水、脱臭、防汚、殺菌、排水処理、藻の成育抑制、及び各種化学反応等に用いられる光触媒を担持した構造体、特に透明性に優れた屋外環境下でも十分な耐久性を有する光触媒複合体、光触媒層形成用塗布液及び光触媒担持構造体に関する。
背景技術：
従来から、光触媒の作用により抗菌、防黴性や有害物質の分解を意図して、光触媒を担体上に担持させてなる光触媒担持構造体が知られている。かかる光触媒担持構造体は、通常担体表面に光触媒成分を含有する光触媒層形成用塗布液を塗布、硬化させることにより光触媒層を形成することにより製造されている。
光触媒層形成用塗布液は、二酸化チタン等の金属酸化物からなる光触媒成分だけでは様々な担体に十分な強度を持って固定することが困難であることからバインダー成分を含有しており、光触媒の酸化作用に耐えうるバインダーとしてシリカゾルが多く用いられてきた。
また、担体（基材あるいは基板）表面に光触媒を含有する被膜または層（以下、「光触媒層」という。）を形成してなる部材（以下、「光触媒担持構造体」という。）を屋外で使用する場合、長期間に渡って風雨にさらされる。このとき、光触媒膜層が耐水性に劣るものである場合には、部分的にあるいは全面的に担体から剥離して、充分な光触媒活性を発揮できない。従って、光触媒担持構造体がより長期間に渡って屋外で使用される場合には、より耐水性が高いことが望まれていた。
さらに、光触媒層が長期間に渡って風雨にさらされた場合には、その透明性が劣化することが知られている。従って、ガラスや透明プラスチック等のような透明な担体上に光触媒膜層を形成する場合には、下値の色や模様を活かすためにも、特に耐水性に優れ、透明度の変化が少ないことが要求されていた。
本発明に用いる細長い形状に結合した球状コロイダルシリカを使用している例が、例えば、特開平１１−１０８０３号公報に光触媒を含有する農業用資材として記載されているが、本発明のような構成は具体的に実施例には記載されていない。
発明の開示：
耐水性および長期耐久性の評価方法としてはＪＩＳＫ５４００やＪＩＳＫ６７４４に規定されているような耐沸騰水試験が知られているが、１時間漬浸した場合でも、剥離がなく、透明性の変化がほとんどないという光触媒触媒層はいままで知られていなかった。
長期間風雨にさらされるような屋外環境で使用される場合の光触媒担持体が解決しなくてはならない課題として、１）１時間沸騰水に漬浸させた後でも、光触媒と担体の接着性が良好であり、かつ光触媒塗膜の透明性の変化が大きくないこと、２）光触媒活性が担体上に担持されることにより大きく低下しないこと、３）屋外における紫外線照射によって担持した光触媒による担体および接着座の劣化がおきず、長期に渡って接着強度を維持し耐久性を保っていることの３点が挙げられる。
本発明は、浄水、脱臭、防汚、殺菌、廃水処理、藻の育成抑制、および各種の化学反応に使用可能で、上記３点の課題を解決しうる光触媒を担持した構造体を提供することを目的とする。
本発明者らは上述の課題を解決すべく鋭意検討した結果、バインダー成分として、アルミニウム、ジルコニウムを主成分とし、特殊な形状を有するシリカゾルを用いることで上記課題を解決できることを見出し本発明を完成するに至った。すなわち、本発明は、
（１）光触媒、コロイダルシリカ粒子を含有する光触媒複合体であって、前記コロイダルシリカ粒子が、球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子であり、該光触媒複合体にさらにジルコニウム化合物およびアルミニウム化合物からなる群から選ばれる少なくとも１種を含有することを特徴とする光触媒複合体、
（２）さらにシリコン化合物を含有することを特徴とする（１）に記載の光触媒複合体、
（３）球状コロイダルシリカ粒子の粒子径が１０〜５０ｎｍであることを特徴とする（１）または（２）に記載の光触媒複合体、
（４）球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子の長さが５０〜４００ｎｍの範囲であることを特徴とする（１）〜（３）のいずれかに記載の光触媒複合体、
（５）球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子が、動的光散乱法による測定粒子径（Ｄ１ｎｍ）と窒素ガス吸着法による測定粒子径（Ｄ２ｎｍ）の比Ｄ１／Ｄ２が５以上であって、このＤ１は４０〜３００ｎｍであり、そして電子顕微鏡観察による５〜２０ｎｍの範囲内の一様な太さで一平面内のみの伸長を有する細長い形状の非晶質コロイダルシリカ粒子であることを特徴とする（１）または（２）に記載の光触媒複合体、
（６）前記ジルコニウム化合物が、ジルコニウムの酸化物、酸化水酸化物、水酸化物、オキシ硝酸塩、オキシ炭酸塩、炭素数１〜４のアルコキシド、及び該アルコキシドの加水分解物からなる群から選ばれる１種または２種以上の混合物であることを特徴とする（１）〜（５）のいずれかに記載の光触媒複合体、
（７）前記アルミニウム化合物が、アルミニウムの酸化物、酸化水酸化物、水酸化物、オキシ硝酸塩、オキシ炭酸塩、炭素数１〜４のアルコキシド、及び該アルコキシドの加水分解物からなる群から選ばれる１種または２種以上の混合物であることを特徴とする（１）〜（６）のいずれかに記載の光触媒複合体、
（８）前記ジルコニウム化合物またはアルミニウム化合物は、１５０℃で乾燥後の比表面積が１００ｍ２／ｇ以上の多孔質ゲルである（６）または（７）に記載の光触媒複合体、
（９）光触媒複合体全体に対して、酸化物に換算して、前記コロイダルシリカ粒子を５〜５０重量％含有し、光触媒を５〜６０重量％含有することを特徴とする（１）〜（８）のいずれかに記載の光触媒複合体、
（１０）光触媒複合体全体に対して、酸化物に換算して、ジルコニウム化合物を、５〜４０重量％含有することを特徴とする（１）〜（９）のいずれかに記載の光触媒複合体、
（１１）光触媒複合体全体に対して、アルミニウム化合物を、酸化物に換算して２０〜９０重量％含有することを特徴とする（１）〜（１０）のいずれかに記載の光触媒複合体に関する。
また、
（１２）光触媒層形成用塗布液であって、球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子が分散したシリカゾル、並びに光触媒粒子及び／またはゾルを含有し、さらに、ジルコニウム化合物およびアルミニウム化合物からなる群から選ばれる少なくとも１種をを含有することを特徴とする光触媒層塗布液、
（１３）さらにポリシロキサンを含有することを特徴とする（１２）に記載の光触媒層塗布液、
（１４）光触媒層形成用塗布液全体に対して、固形分として酸化物換算で、球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子が分散したシリカゾルシリカゾルを０．５〜５重量％、及び光触媒粒子及び／またはゾルを固形分として０．５〜６重量％を含有してなることを特徴とする（１２）または
（１３）に記載の光触媒層形成用塗布液、
（１５）光触媒層形成用塗布液全体に対して、固形分として酸化物換算で、ジルコニウム化合物を０．５〜５重量％、アルミニウム化合物を２〜９重量％からなる群から選ばれる少なくとも１種を含有することを特徴とする（１２）または（１４）に記載の光触媒層形成用塗布液、
（１６）球状コロイダルシリカ粒子の粒子径が１０〜５０ｎｍであることを特徴とする（１２）〜（１５）のいずれかに記載の光触媒形成用塗布液、
（１７）球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子の長さが５０〜４００ｎｍの範囲であることを特徴とする（１２）〜（１６）のいずれかに記載の光触媒形成用塗布液、
（１８）球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子が、動的光散乱法による測定粒子径（Ｄ１ｎｍ）と窒素ガス吸着法による測定粒子径（Ｄ２ｎｍ）の比Ｄ１／Ｄ２が５以上であって、このＤ１は４０〜３００ｎｍであり、そして電子顕微鏡観察による５〜２０ｎｍの範囲内の一様な太さで一平面内のみの伸長を有する細長い形状の非晶質コロイダルシリカ粒子であることを特徴とする（１２）〜（１５）のいずれかに記載の光触媒形成用塗布液、
（１９）前記ジルコニウム化合物が、ジルコニウムの酸化物、酸化水酸化物、水酸化物、オキシ硝酸塩、オキシ炭酸塩、炭素数１〜４のアルコキシド、及び該アルコキシドの加水分解物からなる群から選ばれる１種または２種以上の混合物のゾルであることを特徴とする（１２）〜（１８）のいずれかに記載の光触媒形成用塗布液、
（２０）前記アルミニウム化合物が、アルミニウムの酸化物、酸化水酸化物、水酸化物、オキシ硝酸塩、オキシ炭酸塩、炭素数１〜４のアルコキシド、及び該アルコキシドの加水分解物からなる群から選ばれる１種または２種以上の混合物のゾルであることを特徴とする（１２）〜（１９）のいずれかに記載の光触媒形成用塗布液、
（２１）前記アルミニウム化合物の平均粒子径が２〜５０ｎｍであることを特徴とする（１２）〜（２０）のいずれかに記載の光触媒層形成用塗布液、
（２２）前記アルミニウム化合物の平均粒子径が２〜２０ｎｍである（１２）〜（２０）のいずれかに記載の光触媒層形成用塗布液に関する。
（２３）担体表面に接着層を形成し、さらに該接着層表面に光触媒層を形成してなる光触媒層担持構造体であって、前記光触媒層が、（１）〜（１１）のいすれかに記載の光触媒複合体からなることを特徴とする光触媒層担持構造体に関し、
（２４）前記接着層及び光触媒層を合わせた塗膜の濁度が３％以下であることを特徴とする（２３）に記載の光触媒担持構造体、
（２５）沸騰イオン交換水中で１時間煮沸した後でのＪＩＳＫ５４００に規定された碁盤目テープ法による付着性が評価点数６点以上であることを特徴とする（２３）または（２４）に記載の光触媒担持構造体、
（２６）沸騰イオン交換水中で１時間煮沸した後での接着層及び光触媒層を合わせた塗膜の濁度が３％以下であることを特徴とする（２３）に記載の光触媒担持構造体、
（２７）紫外線強度３ｍＷ／ｃｍ２のブラックライトの光を、温度４０℃、相対湿度９０％の下で５００時間照射した後でのＪＩＳＫ５４００に規定された碁盤目テープ法による付着性が評価点数６点以上であることを特徴とする（２３）に記載の光触媒担持構造体、
（２８）紫外線強度３ｍＷ／ｃｍ２のブラックライトの光を、温度４０℃、相対湿度９０％の下で５００時間照射した後での接着層及び光触媒層を合わせた塗膜の濁度が３％以下であることを特徴とする（２３）に記載の光触媒担持構造体に関する。
本発明の光触媒複合体は、基本的には光触媒成分及び球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子を含有し、さらにジルコニウム化合物及びアルミニウム化合物からなる群から選ばれる少なくとも１種を含有してなることを特徴とする。
光触媒は、粉末状、ゾル状、溶液状など、乾燥・硬化したときに接着層と固着して光触媒活性を示すものであればいずれも使用することができる。特にゾル状で平均粒子径が５０ｎｍ以下、好ましくは２０ｎｍ以下のものを使用する場合には、光触媒層の透明性が向上し直線透過率が高くなるため、透明性を要求されるガラス基板やプラスチック成形体に塗布する場合に好ましい。
また、下地の担体に色や模様が印刷されたものの場合に、こうした透明な光触媒層を塗布すると下地の色や柄を損なうことがない。５０ｎｍ以上では直線透過率が減少し、ヘイズ率が高くなる。ここで、ヘイズ率は、ヘイズ率＝（全光透過率−直線透過率）／全光透過率という関係式で求められる値である。例えば、トイレの窓ガラスは、トイレ内が明るいように全光透過率の高いもので、かつ、内部がはっきりと見えてはいけないのでヘイズ率は高いものである必要がある。
前記光触媒としては、具体的にはＴｉＯ２、ＺｎＯ、ＳｒＴｉＯ３、ＣｄＳ、ＧａＰ、ＩｎＰ、ＧａＡｓ、ＢａＴｉＯ３、ＫＮｂＯ３、Ｆｅ２Ｏ３、Ｔａ２Ｏ５、ＷＯ３、ＳｎＯ２、Ｂｉ２Ｏ３、ＮｉＯ、Ｃｕ２Ｏ、ＳｉＣ、ＳｉＯ２、ＭｏＳ２、ＩｎＰｂ、ＲｕＯ２、ＣｅＯ２等を例示することができ、さらにこれらの光触媒にＰｔ、Ｒｈ、ＲｕＯ２、Ｎｂ、Ｃｕ、Ｓｎ、Ｎｉ、Ｆｅ等の金属もしくは金属酸化物を添加したものを使用することができる。これらの内、耐久性、コスト、光触媒活性を考慮すると酸化チタン（ＴｉＯ２）を主成分とするものが特に好ましく、さらに、光触媒活性を考慮するとアナターゼ型酸化チタンが好ましい。また、太陽光のような紫外線を多く含む光で触媒活性を示す酸化チタンのみならず、貴金属をドープ等して紫外線の少ない室内光においても触媒活性示す酸化チタンを用いることができる。
前記光触媒複合体中の光触媒の含有量は、光触媒複合体全体に対して、酸化物に換算して５重量％〜６０重量％が好ましい。５重量％未満になると光触媒活性が著しく低下する。一方、６０重量％を越える場合には光触媒活性は高くなるものの、接着層との接着性が乏しくなる。
本発明に用いられるコロイダルシリカ粒子は、球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子であることを特徴とし、その形状の具体例として、球状コロイダルシリカ粒子をパールネックレスのパールにみたてるとパールネックレスの一部のような形状を例示することができる。すなわち、球状シリカ粒子を３個以上、好ましくは５個以上、更に好ましくは７個以上連結したものを例示することができる。また、球状コロイダル粒子一つ一つの形状が明確である必要はなく、部分的には筒状に連続して細長い形状をしているものでもよく、さらに、球状コロイダル粒子が結合している必要はなく、粒子全体として細長い形状であるのが好ましい。
細長い形状において、その長さは、５０〜４００ｎｍの範囲が好ましく、その太さを１０〜５０ｎｍの範囲のものが好ましく、全体にわたって太さが均一なものが好ましい。さらに、細長い形状は、ある球状コロイダルシリカ粒子を起点に２次元方向に伸長しているのが好ましい。また、全体として細長い形状であれば、多少分岐構造を有するものでも構わない。
球状コロイダルシリカ粒子が先に述べたようにネックレス状に結合している場合に、その球状コロイダルシリカ粒子の平均粒径は、１０〜５０ｎｍの範囲であるのが好ましい。
以上のような特性を有するコロイダルシリカ粒子として、具体的には、動的光散乱法による測定粒子径（Ｄ１ｎｍ）と窒素ガス吸着法による測定粒子径（Ｄ２ｎｍ）の比Ｄ１／Ｄ２が５以上であって、このＤ１は４０〜３００ｎｍであり、そして電子顕微鏡観察による５〜２０ｎｍの範囲内の一様な太さで一平面内のみの伸長を有する細長い形状の非晶質コロイダルシリカ粒子を例示することができる。このようなコロイダルシリカ粒子が分散したゾルの製造方法として、特開平１−３１７１１５号公報、特開平７−１１８００８号公報に記載されている方法を例示することができる。
本発明に用いられるジルコニウム化合物は光触媒複合体の耐アルカリ性を向上させる目的で添加される。かかるジルコニウム化合物としては、ジルコニウムの酸化物、酸化水酸化物、水酸化物、硝酸塩、オキシ硝酸塩、炭酸塩、オキシ炭酸塩、蓚酸塩、オキシ蓚酸塩、酢酸塩、オキシ酢酸塩、炭素数１〜６のアルコキシド及び該アルコキシドの加水分解生成物からなる群から選ばれた１種又は２種以上の混合物のゲルが好ましい。
ジルコニウムの化合物の好ましい具体例としては、酸化ジルコニウム、オキシ硝酸ジルコニウム、オキシ塩化ジルコニウム、水和酸化ジルコニウム、オキシ水酸化ジルコニウム、水和硝酸ジルコニウム、水和オキシ塩化ジルコニウム、蓚酸ジルコニウム、酢酸ジルコニウム、ジルコニウムテトライソプロポキシド、ジルコニウムテトラブトキシド、ジルコニウムジブトキシドアセチルアセトナート、ジルコニウムジブトキシドラクテート、ジルコニウムブトキシドの加水分解生成物、ジルコニウムイソプロポキシドの加水分解生成物を挙げることができる。
アルミニウムの化合物は、光触媒複合体の耐アルカリ性をさらに向上させ、ヘイズ率を下げる目的で添加される。アルミニウム化合物としては、アルミニウムの酸化物、酸化水酸化物、水酸化物、硝酸塩、オキシ硝酸塩、炭酸塩、オキシ炭酸塩、蓚酸塩、オキシ蓚酸塩、酢酸塩、オキシ酢酸塩、炭素数１〜６のアルコキシド、及び該アルコキシドの加水分解生成物からなる群から選ばれた１種又は２種以上の混合物が好ましい。
アルミニウムの化合物の好ましい具体例として、酸化アルミニウム、酸化水酸化アルミニウム、水酸化アルミニウム、水和酸化アルミニウム、ベーマイト、硝酸アルミニウム、オキシ硝酸アルミニウム、炭酸アルミニウム、オキシ炭酸アルミニウム、蓚酸アルミニウム、オキシ蓚酸アルミニウム、酢酸アルミニウム、オキシ酢酸アルミニウム、アルミニウムトリイソプロポキシド、アルミニウムトリブトキシド、アルミニウムブトキシドアセチルアセトナート、アルミニウムブトキシドラクテート、アルミニウムブトキシドの加水分解生成物、アルミニウムイソプロポキシドの加水分解生成物等を挙げることができる。
光触媒と共に用いられるジルコニウム化合物またはアルミニウム化合物は、平均粒子径が２ｎｍ〜５０ｎｍ、好ましくは２ｎｍ〜２０ｎｍのゾルを使用するのが好ましい。このいような粒子径のものを使用する場合には、光触媒層の透明性が向上し、直線透過率が高くなるため、特に透明性を要求されるガラス基板やプラスチック成形体に塗布する場合に好ましい。また、下地の担体に色や模様が印刷されたものの場合に、こうした透明な光触媒層を塗布すると下地の色や柄を損なうことがない。また、平均粒子径が５０ｎｍ以上のものを用いる場合には、直線透過率が減少し、ヘイズ率が高くなる。
前記光触媒複合体中のジルコニウムまたはアルミニウムの、酸化物、酸化水酸化物、水酸化物は、１５０℃で乾燥後の比表面積が１００ｍ２／ｇ以上の多孔質ゲルを使用するのが好ましい。多孔質ゲルは吸着性を有しており、光触媒活性を高める効果を有する。
前記光触媒複合体中のジルコニウム化合物の含有量は、光触媒複合体全体に対して、酸化物に換算して５〜４０重量％であるのが好ましい。５重量％未満では光触媒層の耐アルカリ性に乏しくなる。一方、４０重量％を越えると透明性が悪くなる。
前記光触媒複合体のアルミニウム化合物の含有量は、光触媒複合体全体に対して、酸化物に換算して２０〜９０重量％であるのが好ましい。２０重量％未満では光触媒層のヘイズ率の上昇を抑制する効果及び耐アルカリ性を高める効果に乏しくなる。一方、添加量が９０重量％を越えると光触媒活性が低下する。
前記光触媒複合体中のジルコニウム化合物及びアルミニウム化合物の含有量は、合計でこれらの酸化合物に換算して４０〜９５重量％が好ましい。４０重量％未満では、接着層との接着が不十分となり、９５重量％を越えると、添加できる光触媒の量が減少するため光触媒活性の低下が著しい。
前記光触媒複合体中に、さらにシリコン化合物を含有することより膜強度が向上する。シリコン化合物としては、
ＳｉＣｌｎ１（ＯＨ）ｎ２Ｒ１ｎ３（ＯＲ２）ｎ４
で表されるシリコンアルコキシドまたはそれらの加水分解生成物である。
ここで、Ｒ１はメチル、エチル、プロピル、イソプロピル、ブチル、ｓ−ブチル、ｔ−ブチル、ヘキシル、オクチル、アミノメチル、アミノエチル、カルボキシメチル、カルボキシエチル、クロロメチル、クロロエチル、クロロプロピル基等の（アミノ基、カルボキシル基又は塩素原子で置換されていてもよい）炭素数１〜８のアルキル基を表す。
Ｒ２は、メチル、エチル、プロピル、イソプロピル、ブチル、ｓ−ブチル、ｔ−ブチル、ヘキシル基等の炭素数１〜８のアルキル基、又はメトキシメチル、エトキシメチル、プロポキシメチル、イソプロポキシメチル、ブトキシメチル、メトキシエチル、エトキシメチル、プロポキシエチル、メトキシプロピル、メトキシブチル基等のアルコキシ基で置換された炭素数１〜８のアルキル基を表す。またｎ１、ｎ２及びｎ３は０、１又は２を表し、ｎ４は２から４の整数を表し、かつｎ１＋ｎ２＋ｎ３＋ｎ４＝４である。
前記式で表されるシリコンアルコキシドの好ましい具体例としては、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン等を挙げることができる。
前記光触媒複合体中のシリコン化合物の含有量は、光触媒複合体全体に対して、酸化物に換算して１〜２０重量％であるのが好ましい。
またこれらの多成分に、塗膜強度を向上させる目的で、更にスズ、ニオブ、タンタルの酸化物あるいはこれらの水酸化物を含有させることもできる。その場合においては、光触媒層中のアルミニウムの酸化物、酸化水酸化物もしくは水酸化物のの含有量が前記耐アルカリ性向上のために添加する含有量の範囲内であれば、極めて優れた耐アルカリ性を示すものとすることができる
本発明の光触媒層形成用塗布液は、球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子が分散したシリカゾル、並びに光触媒粒子及び／またはゾルを含有し、さらに、ジルコニウム化合物およびアルミニウム化合物からなる群から選ばれる少なくとも１種をを含有することを特徴とする。
前記光触媒層形成用塗布液に含まれる、球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子が分散したシリカゾル、ジルコニウム化合物、アルミニウム化合物及び光触媒の具体例としては、前記光触媒複合体に含まれるコロイダルシリカ粒子、ジルコニウム化合物、アルミニウム化合物及び光触媒の好ましいものとして列記したものと同様なものを用いることができる。
前記ジルコニウム化合物、アルミニウム化合物及び光触媒はゾルの形で用いるのが好ましい。ゾルを使用する場合には、安定化のために光触媒塗布液中へ酸やアルカリの解膠剤を添加することもできる。またゾル懸濁液中に、接着性や操作性を良くする目的で、光触媒に対して５重量％以下の界面活性剤等を添加することもできる。
光触媒層形成用塗布液に含まれる各成分の量は、塗布液全体に対して、固形分として酸化物換算で、球状コロイダルシリカ粒子が細長い形状に結合したコロイダルシリカ粒子が分散したシリカゾルシリカゾルを０．５〜５重量％、及び光触媒粒子及び／またはゾルを固形分として０．５〜６重量％であるのが好ましく、光触媒層形成用塗布液全体に対して、固形分として酸化物換算で、ジルコニウム化合物を０．５〜５重量％、アルミニウム化合物を２〜９重量％であるのが好ましい。
光触媒複合体にシリコン化合物を含有させる場合には、光触媒層形成用塗布液全体に対して、固形分として酸化物換算で、シリコン化合物を０．００１〜５重量％含有させるのが好ましい。シリコン化合物としては例えば炭素数１〜５のアルコキシ基を有するシリコンアルコキシドの加水分解物あるいは該加水分解物生成物が好ましい。シリコンアルコキシドのアルコキシ基の炭素数が６を超えると、加水分解速度が非常に遅くなる。また、部分的に塩素を含んだシリコンアルコキシドを加水分解したポリシロキサンを使用することもできるが、塩素を多量に含有したポリシロキサンを使用する場合には、不純物の塩素イオンにより、担体が腐食されたり、接着性が低下するおそれがある。
かかるシリコンアルコキシドとしては、例えば、次式で表される化合物が好ましく使用できる。
ＳｉＣｌｎ１（ＯＨ）ｎ２Ｒ１ｎ３（ＯＲ２）ｎ４
ここで、Ｒ１はメチル、エチル、プロピル、イソプロピル、ブチル、ｓ−ブチル、ｔ−ブチル、ヘキシル、オクチル、アミノメチル、アミノエチル、カルボキシメチル、カルボキシエチル、クロロメチル、クロロエチル、クロロプロピル基等の（アミノ基、カルボキシル基又は塩素原子で置換されていてもよい）炭素数１〜８のアルキル基を表す。
Ｒ２は、メチル、エチル、プロピル、イソプロピル、ブチル、ｓ−ブチル、ｔ−ブチル、ヘキシル基等の炭素数１〜８のアルキル基、又はメトキシメチル、エトキシメチル、プロポキシメチル、イソプロポキシメチル、ブトキシメチル、メトキシエチル、エトキシメチル、プロポキシエチル、メトキシプロピル、メトキシブチル基等のアルコキシ基で置換された炭素数１〜８のアルキル基を表す。またｎ１、ｎ２及びｎ３は０、１又は２を表し、ｎ４は２から４の整数を表し、かつｎ１＋ｎ２＋ｎ３＋ｎ４＝４である。
前記式で表されるシリコンアルコキシドの好ましい具体例としては、Ｓｉ（ＯＣＨ３）４、Ｓｉ（ＯＣ２Ｈ５）４、Ｓｉ（ＯＣ３Ｈ７）４、Ｓｉ（ＯＣ４Ｈ９）４、Ｓｉ（ＯＣ５Ｈ１１）４、Ｓｉ（ＯＣ６Ｈ１３）４、ＳｉＣＨ３（ＯＣＨ３）３、ＳｉＣＨ３（ＯＣ２Ｈ５）３、ＳｉＣＨ３（ＯＣ３Ｈ７）３、ＳｉＣＨ３（ＯＣ３Ｈ７）３、ＳｉＣＨ３（ＯＣ４Ｈ９）３、ＳｉＣｌ（ＯＣＨ３）３、ＳｉＣｌ（ＯＣ２Ｈ５）３、ＳｉＣｌ（ＯＣ３Ｈ７）３、ＳｉＣｌ（ＯＣ４Ｈ９）３、ＳｉＣｌ（ＯＣ６Ｈ１３）３、ＳｉＣｌ（ＯＨ）（ＯＣＨ３）２、ＳｉＣｌ（ＯＨ）（ＯＣ２Ｈ５）２、ＳｉＣｌ（ＯＨ）（ＯＣ３Ｈ７）２、ＳｉＣｌ（ＯＨ）（ＯＣ４Ｈ９）２、ＳｉＣｌ２（ＯＣＨ３）２、ＳｉＣｌ２（ＯＣ２Ｈ５）２等を挙げることができる。
光触媒層形成用塗布液の調製方法としては、（ａ）ジルコニウム又はアルミニウムの酸化物、酸化水酸化物もしくは水酸化物のゾル溶液、光触媒、コロイダルシリカゾル等を混合する方法、ジルコニウム又はアルミニウムの酸化物、酸化水酸化物もしくは水酸化物のゾルの前駆体溶液の状態で光触媒とコロイダルシリカゾル等を混合する方法、（ｂ）ジルコニウム又はアルミニウムの酸化物、酸化水酸化物もしくは水酸化物のゾル溶液及びコロイダルシリカゾルと光触媒を形成させるためのゾルや溶液等を混合する方法等、光触媒層中に均一に混合される方法であれば、いずれの方法も採用できる。また、（ｃ）ジルコニウム又はアルミニウムの酸化物、酸化水酸化物もしくは水酸化物のゾルの前駆体溶液中に、光触媒粒子又はゾル、及びコロイダルシリカゾル等を分散し、コート時に加水分解や中和分解してゾル化させることもできる。
用いられる溶媒としては、例えば、水、メタノール、エタノール、プロピルアルコール、イソプロピルアルコール、ブタノール、ｔ−ブタノール等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノン等のケトン類、ジエチルエーテル、メチルセルソルブ、テトラヒドロフラン等のエーテル類、ベンゼン、トルエン、キシレン等の芳香族炭化水素、ジクロロメタン、クロロホルム等のハロゲン化炭化水素、サクサンエチル、酢酸プロピル、酢酸ブチル等のエステル類、ペンタン、ヘキサン、シクロヘキサン等の飽和炭化水素等を挙げることができる。また、これらの２種以上を混合して用いることもできる。これらの内、水−アルコール系溶媒が特に好ましい。
本発明に係る光触媒を担持した構造体は、光触媒層と担体の間に接着層を設けた構造を有する。光触媒層と担体との間に設けた接着層は、下地の担体を光触媒作用による劣化から保護する作用と光触媒層を担体に強固に接着させる作用を有しており、また接着層自身が光触媒作用による劣化を受けにくいという特徴をもつ。
前記担体は、接着剤層を介して光触媒を担持可能なものであれば特に限定されない。例えば、セラミックス、無機質材料、担体材質が熱をかけられない有機高分子体や熱や水等により酸化腐食し易い金属であっても、この接着層と光触媒層を設けた構造体を得ることができる。また、担体形状としては、フィルム状、シート状、板状、管状、繊維状、網状等どのような複雑な形状のものも使用可能である。担体の厚さとしては１０μｍ以上のものであれば強固に担持することができるので好ましい。さらに、担体と接着層との密着性を良くするために、表面を放電処理やプライマー処理等の易接着処理を施した担体を用いることができる。
接着層の材質としては、担体を光触媒作用による劣化から保護し、さらに光触媒層を強固に固定できるものであれば特に制限されないが、具体的には（１）シリコン含有量が酸化物に換算して２〜１０重量％の（アクリルシリコン樹脂、エポキシシリコン樹脂、ポリエステルシリコン樹脂）等のシリコン変性樹脂、（２）ポリシロキサンを酸化物に換算して３〜９０重量％含有する樹脂、又は（３）コロイダルシリカを酸化物に換算して５〜９０重量％含有した樹脂を使用することができる。これらの樹脂は光触媒を強固に接着し、担体を光触媒から保護するのに適当である。
シリコン含有量が酸化物に換算して２重量％未満のアクリルシリコン樹脂等のシリコン変性樹脂やポリシロキサン含有量が酸化物に換算して３重量％未満の樹脂、コロイダルシリカ含有量が酸化物に換算して５重量％未満の樹脂では、光触媒層との接着が悪くなる。また、接着層が光触媒により劣化し、光触媒層が剥離し易くなる。シリコン含有量が酸化物に換算して１０重量％を超えるアクリル−シリコン樹脂等のシリコン変性樹脂やポリシロキサン含有量が酸化物に換算して９０重量％を超える樹脂、コロイダルシリカ含有量が酸化物に換算して９０重量％を超える樹脂では、担体との密着性が低下する。
またシリコンを導入する樹脂としては、アクリル樹脂、エポキシ樹脂、ポリエステル樹脂、アルキド樹脂、ウレタン樹脂等を例示することができる。これらの内、アクリル樹脂、エポキシ樹脂、ポリエステル樹脂が、成膜性、強靭性、担体との密着性の点で特に好ましい。これらの樹脂は、溶液状であってもエマルジョンタイプであってもどちらでも使用できる。また、架橋剤等の添加物が含まれていてもよい。
前記接着層の樹脂に含まれるポリシロキサンが炭素数１〜５のアルコキシ基を有するシリコンアルコキシドの加水分解物あるいは該加水分解物生成物である場合には、接着性及び耐久性がより向上した担持構造体を得ることができる。シリコンアルコキシドのアルコキシ基の炭素数が６を超えると、加水分解速度が非常に遅いので、樹脂中で硬化させるのが困難になり、接着性や耐久性が悪くなる。また、部分的に塩素を含んだシリコンアルコキシドを加水分解したポリシロキサンを使用することもできるが、塩素を多量に含有したポリシロキサンを使用する場合には、不純物の塩素イオンにより、担体が腐食されたり、接着性が低下するおそれがある。
かかるシリコンアルコキシドとしては、例えば、次式で表される化合物が好ましく使用できる。
ＳｉＣｌｎ１（ＯＨ）ｎ２Ｒ１ｎ３（ＯＲ２）ｎ４
ここで、Ｒ１はメチル、エチル、プロピル、イソプロピル、ブチル、ｓ−ブチル、ｔ−ブチル、ヘキシル、オクチル、アミノメチル、アミノエチル、カルボキシメチル、カルボキシエチル、クロロメチル、クロロエチル、クロロプロピル基等の（アミノ基、カルボキシル基又は塩素原子で置換されていてもよい）炭素数１〜８のアルキル基を表す。
Ｒ２は、メチル、エチル、プロピル、イソプロピル、ブチル、ｓ−ブチル、ｔ−ブチル、ヘキシル基等の炭素数１〜８のアルキル基、又はメトキシメチル、エトキシメチル、プロポキシメチル、イソプロポキシメチル、ブトキシメチル、メトキシエチル、エトキシメチル、プロポキシエチル、メトキシプロピル、メトキシブチル基等のアルコキシ基で置換された炭素数１〜８のアルキル基を表す。またｎ１、ｎ２及びｎ３は０、１又は２を表し、ｎ４は２から４の整数を表し、かつｎ１＋ｎ２＋ｎ３＋ｎ４＝４である。
前記式で表されるシリコンアルコキシドの好ましい具体例としては、Ｓｉ（ＯＣＨ３）４、Ｓｉ（ＯＣ２Ｈ５）４、Ｓｉ（ＯＣ３Ｈ７）４、Ｓｉ（ＯＣ４Ｈ９）４、Ｓｉ（ＯＣ５Ｈ１１）４、Ｓｉ（ＯＣ６Ｈ１３）４、ＳｉＣＨ３（ＯＣＨ３）３、ＳｉＣＨ３（ＯＣ２Ｈ５）３、ＳｉＣＨ３（ＯＣ３Ｈ７）３、ＳｉＣＨ３（ＯＣ３Ｈ７）３、ＳｉＣＨ３（ＯＣ４Ｈ９）３、ＳｉＣｌ（ＯＣＨ３）３、ＳｉＣｌ（ＯＣ２Ｈ５）３、ＳｉＣｌ（ＯＣ３Ｈ７）３、ＳｉＣｌ（ＯＣ４Ｈ９）３、ＳｉＣｌ（ＯＣ６Ｈ１３）３、ＳｉＣｌ（ＯＨ）（ＯＣＨ３）２、ＳｉＣｌ（ＯＨ）（ＯＣ２Ｈ５）２、ＳｉＣｌ（ＯＨ）（ＯＣ３Ｈ７）２、ＳｉＣｌ（ＯＨ）（ＯＣ４Ｈ９）２、ＳｉＣｌ２（ＯＣＨ３）２、ＳｉＣｌ２（ＯＣ２Ｈ５）２等を挙げることができる。
これらシリコン変性樹脂のシリコンを導入する方法としは、エステル交換反応、シリコンマクロマーや反応性シリコンモノマーを用いたグラフト反応、ヒドロシリル化反応、ブロック共重合法等種々あるが、どのような方法で得られたものも使用できる。
例えば、ポリシロキサンの樹脂への導入方法としては、（１）シリコンアルコキシドをモノマーの状態で樹脂溶液と混合し、接着層形成時に空気中の水分で加水分解させる方法、（２）予めシリコンアルコキシドの部分加水分解物を樹脂と混合し、更に、接着剤層形成時に空気中の水分で加水分解する方法等種々あるが、樹脂と均一に混合できる方法ならどのような方法でも良い。
また、シリコンアルコキシドの加水分解速度を調整するために、酸や塩基触媒を少量添加してもよい。ポリシロキサンの樹脂への添加量は、担体に光触媒層を強固に接着させるためには酸化物に換算して３〜９０重量％が好ましい。
ポリシロキサンを導入させる樹脂としては、アクリル樹脂、エポキシ樹脂、ポリエステル樹脂、ウレタン樹脂、アルキド樹脂等どのような樹脂も使用できる。これらのうち、アクリル樹脂、エポキシ樹脂、ポリエステル樹脂又はこれらの混合樹脂は、シリコン変性樹脂とした場合、耐久性や耐アルカリ性の点で好ましい。
接着層がコロイダルシリカを含有する場合、コロイダルシリカの粒子径は１０ｎｍ以下であるのが好ましい。粒子径が１０ｎｍ以上になると、接着層中の樹脂は光触媒により劣化し易くなるばかりか、光触媒層と接着層との接着も悪くなる。
コロイダルシリカを樹脂に導入する方法としては、樹脂溶液とコロイダルシリカ溶液を混合後、塗布−乾燥して保護膜を形成する方法が最も簡便である。その他、コロイダルシリカを分散した状態で樹脂を重合させたたものを使用することもできる。
また、コロイダルシリカと樹脂との接着性および分散性を良くするために、シランカップリング剤で処理されたコロイダルシリカを用いることもできる。
コロイダルシリカの樹脂への添加量は、担体に光触媒層を強固に接着させるためには酸化物に換算して５〜９０重量％が好ましい。
コロイダルシリカを導入する樹脂としては、アクリル樹脂、エポキシ樹脂、ウレタン樹脂、ポリエステル樹脂、アルキド樹脂等どのような物でも使用可能である。これらの樹脂の中で、アクリル樹脂、エポキシ樹脂及びポリエステル樹脂が、シリコン変性樹脂とした場合に耐久性や耐アルカリ性に優れたものを得ることができるため特に好ましい。
またコロイダルシリカは、珪酸ナトリウム水溶液を陽イオン交換することにより得られるシリカゾルであっても、シリコンアルコキシドを加水分解して得られるシリカゾルであっても、どのようなものでも使用することができる。
さらに本発明においては、ポリシロキサン及びコロイダルシリカの両方を含有する樹脂を接着層として使用することができる。その場合、接着層中のポリシロキサンおよびコロイダルシリカの含有量の合計が酸化物に換算して前記耐アルカリ性向上を示す含有量の範囲内であれば、同様に優れた耐アルカリ性を示すものとすることができる
接着層に使用する樹脂がコロイダルシリカを含有する樹脂若しくはポリシロキサンを含有する樹脂の場合、そのコロイダルシリカやポリシロキサンの粒子径は１０ｎｍ以下が望ましい。コロイダルシリカやポリシロキサンの粒子径が１０ｎｍを越えるものであると、分散性が悪くなり、接着層の透光性が低下するため接着層と光触媒層の合計の波長５５０ｎｍの全光線透過率は７０％以下となる場合がある。
なお接着層樹脂には光触媒作用による劣化を抑える目的で、光安定化剤及び／又は紫外線吸収剤をさらに添加することができる。使用することができる光安定化剤としてはヒンダードアミン系が好ましいが、その他の物でも使用可能である。紫外線吸収剤としてはトリアゾール系等が使用できる。これらの添加量は、樹脂に対して、０．００５重量％〜１０重量％、好ましくは０．０１重量％〜５重量％である。また、接着層上をシラン系もしくはチタン系カップリング剤で処理することにより、光触媒層との接着性を高めることも好ましい。
接着層を担体上に形成する方法としては、接着剤樹脂溶液を印刷法、シート成形法、スプレー吹き付け法、ディップコーティング法、スピンコーティング法等でコート、乾燥・硬化させる方法を例示することができる。乾燥温度は、溶媒や樹脂の種類によっても異なるが、一般的に５０℃〜３００℃程度が好ましい。
接着層の厚さは、光触媒層との良好な接着を得るためには０．１μｍ〜２０μｍ程度が望ましい。接着層の厚みが０．１μｍ以下であると、光触媒層を強固に接着させる働きが弱くなる。一方、厚みが２０μｍ以上の場合は特に問題はないものの、実際の塗布加工を考慮すると２０μｍ以上にするメリットは少ない。
光触媒層は、前記光触媒層形成用塗布液を接着層表面に印刷法、シート成形法、スプレー吹き付け法、ディップコーティング法、スピンコーティング法等でコートし、乾燥・硬化させることにより形成することができる。乾燥・硬化時の好ましい温度は、担体材質及び接着層中の樹脂材質によっても異なるが、通常５０℃〜３００℃程度である。
光触媒層の厚みは厚い方が光触媒活性は高くなるが、２０μｍを越えると光触媒活性は飽和する一方で、実際の塗布加工において困難となる場合が多く、また光触媒層の光透過率が低下するため２０μｍ以下が好ましい。一方、光触媒の厚さが０．１μｍ未満になると、透光性は良くなるものの、光触媒が利用する紫外線をも透過してしまうために高い活性は望めなくなる。
光触媒層の厚さを０．１μｍ以上２０μｍ以下とし、しかも平均粒子が５０ｎｍ以下の光触媒粒子、及びアルミニウムの酸化物もしくは水酸化物のゲルを用いることにより、光触媒層と接着層の合計の波長５５０ｎｍの全光線透過率は８０％以上で、ヘイズ率が２％以下のものを得ることができる。かかる光触媒担持構造体は、透明な担体を用いる場合、透過した可視光線を照明として利用でき、また担体が不透明な場合でも、担体上の柄を損なうことがないので装飾性の上でも優れたものとなる。
このようにして得られる本発明の光触媒担持構造体は、前記接着層及び光触媒層を合わせた塗膜の濁度が３％以下であることを特徴とする。この場合、濁度とは、先に述べたヘイズ率と同じ意味で用いられる。
さらに、沸騰イオン交換水中で１時間煮沸した後でのＪＩＳＫ５４００に規定された碁盤目テープ法による付着性が評価点数６点以上であることを特徴とする。また、沸騰イオン交換水中で１時間煮沸した後での接着層及び光触媒層を合わせた塗膜の濁度が３％以下であることを特徴とし、紫外線強度３ｍＷ／ｃｍ２のブラックライトの光を、温度４０℃、相対湿度９０％の下で５００時間照射した後でのＪＩＳＫ５４００に規定された碁盤目テープ法による付着性が評価点数６点以上であることを特徴とし、紫外線強度３ｍＷ／ｃｍ２のブラックライトの光を、温度４０℃、相対湿度９０％の下で５００時間照射した後での接着層及び光触媒層を合わせた塗膜の濁度が３％以下であることを特徴とする。
本発明の光触媒を担持した構造体は、建築用塗料、壁紙、窓ガラス、ブラインド、カーテン、カーペット、照明器具、照明灯、道路灯、トンネル照明灯、高速道や新幹線の遮音壁、ブラックライト、船底・漁網防汚塗料、水処理用充填剤、農ビフィルム、防草シート、包装資材等に使用できる。特に高温多湿の環境下や屋外の環境下で使用される場合に、その優れた耐久性や透明性などの特性を発揮する。
発明を実施するための最良の形態：
次に、実施例により本発明をさらに詳細に説明するが、本発明は、実施例に限定されるものでない。
１）光触媒層形成用塗布液
（１）光触媒
光触媒触媒は次のものを使用した。
（Ｔ−１）硝酸酸性酸化チタンゾル（結晶粒子径８ｎｍ）
（２）シリカゾル
シリカゾルは次のものを使用した。
（Ｓ−１）ネックレス状コロイダルシリカ（日産化学製スノーテックスＰＳ）
（３）アルミニウム化合物
アルミニウム化合物は次のものを使用した。
（Ａ−１）酸化水酸化アルミニウム（ベーマイト）微粒子（川研ファインケミカル製アルミゾル１０）
（４）ジルコニウム化合物
ジルコニウム化合物は次のものを使用した。
（Ｚ−１）和光純薬製試薬特級オキシ硝酸ジルコニウム６水和物を水に溶解し１０％水溶液とした後、１２時間加熱して半量の水を常圧で留去して得られた液をオキシ硝酸ジルコニウム液として使用した。
（５）光触媒層形成用塗布液の調製
上記酸化チタン光触媒、ゾル溶液および化合物液を、ｐＨ１．５〜９の適当な範囲に調製して、混合し、所定量の界面活性剤を加えて光触媒層形成用塗布液を得た。
２）光触媒担持構造体の製造
（１）担体
（ＴＡ）ソーダライムガラス板
（ＴＢ）透明アクリル板
（ＴＣ）アルミ板
（２）接着剤層接着層中に含有するポリシロキサンは、次のものを使用した。
（ＰＳ−１）信越化学製シリコンテトラメトキシドモノマー
（ＰＳ−２）コルコート製ポリメトキシシロキサン商品名メチルシリケート５１
（ＰＳ−３）コルコート製ポリエトキシシロキサン商品名エチルシリケート４０接着層中に含有するコロイダルシリカとして、次のものを使用した。
（ＫＳ−１）触媒化成（株）製商品名カタロイドＳＩ−３５０、粒子径７−９ｎｍ
（ＫＳ−２）日産化学（株）製商品名スノーテックスＳＴ−ＸＳ、粒子径４−６ｎｍポリシロキサンもしくはコロイダルシリカを導入する樹脂溶液としては次のものを使用した。尚、シリコン含有量は樹脂固形分中のＳｉＯ２に換算して表示した。
（Ｊ−１）シリコン含有量３重量％のアクリル−シリコン樹脂キシレン溶液
（Ｊ−２）シリコン含有量１０重量％のアクリル−シリコン樹脂のキシレンイソプロパノール溶液
（Ｊ−３）シリコン含有量３重量％のアクリル−シリコンエマルジョン樹脂水溶液
（Ｊ−４）シリコン含有量３重量％のエポキシ−シリコン樹脂メチルエチルケトン溶液
（Ｊ−５）シリコン含有量３重量％のポリエステル−シリコン樹脂酢酸エチル溶液
（Ｊ−６）アクリルエマルジョン樹脂水溶液
ポリシロキサンもしくはコロイダルシリカを樹脂溶液と混合、濃度調製し、接着層形成用溶液を得た。接着層は、厚さが２μｍ以下の時や担体形状が平板以外の時はディッピング法で、担体が平板で厚さが２μｍ以上の場合には、ベーカーアプリケーターにより形成した。なお、接着層の乾燥は、担体の材質が、（ＴＢ）の場合８０℃で、それ以外は１２０℃で行った。
（３）光触媒層は、担体の厚みが２μｍ以下の場合や担体形状が平板以外の場合は、ディッピング法で、担体が平板で厚みが２μｍ以上の場合は、バーコーターを用いて、背着座位相表面に塗工形成した。光触媒層の乾燥は、接着層を乾燥するのと同じ温度で行った。
３）光触媒担持構造体の性能試験
上記で得られた光触媒を担持した各試料を用いて、以下の性能試験を行った。（１）光触媒活性の評価試験
大きさ７０ｍｍ×７０ｍｍに切り出した光触媒を担持した試料を、容量４リットルのパイレックス（登録商標）製ガラス容器中に設置した。この容器中に空気とアルデヒドの混合ガスを、アルデヒド濃度が２００ｐｐｍとなるように加えた。次いで、担持試料に紫外線強度２ｍＷ／ｃｍ２のブラックライト（ＦＬ１５ＢＬＢ、東芝ライテック製）の光を３時間照射後、容器内部のアルデヒドガス濃度をガスクロマトグラフにより測定し、その減少量により光触媒活性を評価した。
評価基準は下記の通りである。
３時間照射後のアルデヒドガス濃度の減少量による性能評価
１００ｐｐｍ以上 Ａ
５０〜１００ｐｐｍ Ｂ
２０〜５０ｐｐｍ Ｃ
（２）付着性評価試験
光触媒を担持した試料表面に、切り傷によって２ｍｍの間隔で２５個のマス目を形成し、ＪＩＳＫ５４００に規定する碁盤目テープ法試験により付着性の評価を行った。評価点数は、ＪＩＳＫ５４００に記載の基準で行った。
（３）耐沸騰水性評価試験
ＪＩＳＫ５４００に規定する耐沸騰水試験に準拠して耐沸騰水試験を行った。ただし、漬浸時間を１時間とした。
（４）ヘイズ率の測定
接着層及び光触媒層を担持する前の担体をリファレンスとして、担持した試料の波長５５０ｎｍの全光線透過率、及びヘイズ率を自記分光光度計（日立製作所（株）製Ｕ−４０００型）で測定した。
（５）耐久性試験
光触媒を担持した試料にブラックライトで紫外線強度３ｍＷ／ｃｍ２の光を、温度４０℃、相対湿度９０％の恒温恒湿槽内で５００時間照射後、ＪＩＳＫ５４００に規定の碁盤目テープ法による付着性を測定し、耐久性の評価とした。評価点数は、付着性評価と同じとした。
以下の第１表に各材料の種類や量などを変えた実施例および比較例の様態を、第２表に得られた光触媒担持構造体の性能試験結果をまとめた。
また比較例３は、光触媒層に中のジルコニアゾルが多すぎる場合である。初期のヘイズ率が高い。
実施例１〜３は、接着層にアクリル−シリコン樹脂を使用し、ネックレス状コロイダルシリカを使用した光触媒層を使用した例である。これらの試料は耐沸騰水性試験による評価は良好であり、耐久性も良好であった。
実施例４〜１４は、接着層にポリシロキサンを含有したアクリル−シリコン樹脂を使用し、ネックレス状コロイダルシリカを使用した光触媒層を使用した例である。
実施例７、８、１１は、透明アクリル板上に担持した例である。これらの試料も耐久性も良好であった。
また、接着層の樹脂として、ポリシロキサンを導入したエポキシ−シリコン樹脂（実施例１６）やポリエステル−シリコン樹脂（実施例１７）、アクリル樹脂（実施例１８）を用いた場合にも良好な性能を示した。
実施例１９〜２６は接着層にコロイダルシリカを含有した樹脂を使用したものであり、触媒活性、耐沸騰水性、耐久性は良好であった。
実施例１〜２６で得られた試料で、高温高湿下のブラックライトによる耐久性試験、耐沸騰水試験およびサンシャインカーボンアークウエザーメーター（スガ試験機性、ＷＥＬ−ＳＵＮ−ＨＣＨ型）による促進耐光性試験にかけた試料を、再度光触媒活性を初期と同様の方法によりアセトアルデヒドガスの分解量により調べた。いずれの試料についても初期の光触媒活性を維持していることが判った。
実施例２７〜３１はソーダライムガラス板上に、接着層を介さず直接に、光触媒層を成膜した後、２００℃で乾燥を行ったものであり、触媒活性、耐沸騰水性、耐久性は良好であった。
実施例２７〜３１で得られた試料を、高温高湿下のブラックライトによる耐久性試験、耐沸騰水試験およびサンシャインカーボンアークウエザーメーター（スガ試験機性、ＷＥＬ−ＳＵＮ−ＨＣＨ型）による促進耐光性試験に２０００時間かけた試料を、再度光触媒活性を初期と同様の方法によりアセトアルデヒドガスの分解量により調べた。いづれの試料についても初期の光触媒活性を維持していることが判った。
実施例２７〜３１で得られた試料を、サンシャインカーボンアークウエザーメーター（スガ試験機性、ＷＥＬ−ＳＵＮ−ＨＣＨ型）による促進耐光性試験に２０００時間かけた試料のヘイズ率を測定したところ、濁度がいづれも２％以内の値を示し、高透明性を維持していることが判った。
実施例３２
光触媒層薬剤にさらにポリメトキシシロキサン（試薬）を酸化物換算で全固形分に対して１０重量％となるように添加した以外は、実施例１２に準じて成膜した。光触媒はＢ評価であった。しかし、大平理化工業（株）製のラビングテスターを用いて、フェルト摩耗試験を行ったところ、実施例１２の塗膜は２００往復で剥離が認められたのに対して、実施例３２の塗膜は４００往復でも剥離が認められなかった。
実施例３３
光触媒層薬剤にさらにポリメトキシシロキサン（試薬）を酸化物換算で全固形分に対して２０重量％となるように添加した以外は、実施例１４に準じて成膜した。光触媒はＣ評価であった。しかし、大平理化工業（株）製のラビングテスターを用いて、フェルト摩耗試験を行ったところ、実施例１４の塗膜は１００往復で剥離が認められたのに対して、実施例３３は４００往復でも剥離が認められなかった。
産業上の利用可能性：
以上説明したように、本発明の光触媒複合体は光触媒活性が非常に高く、透明性に優れるものである。
本発明の光触媒層形成用塗布液は、保存安定性に優れ、簡便に光触媒層を形成することができる。また得られる光触媒層は、可視光を透過する透明なものも得られるので、担体の柄を損なうことがなく触媒を担持することができ、汎用樹脂や天然繊維などの幅広い担体に装飾性を損なうことがなく優れた活性を有する光触媒担持構造体を得ることができる。
本発明の光触媒担持構造体は、光触媒が担体に強固に接着されており、光触媒活性が非常に高く、しかも光触媒作用により担体が劣化したり、光触媒が脱離したりすることがない。
また、本発明の光触媒担持構造体は、光照射下でも長期間使用できるものである。また、耐アルカリ性試験の評価も良好で、サンシャインカーボンアークウェザーメーターによる促進耐候性試験後においても高い付着性を保っていることから、高温多湿の環境下や屋外の環境下で使用することができる。Technical field:
The present invention is a structure carrying a photocatalyst used for water purification, deodorization, antifouling, sterilization, wastewater treatment, growth control of algae, various chemical reactions, etc., particularly durability sufficient even in an outdoor environment with excellent transparency. The present invention relates to a photocatalyst complex having photocatalyst, a coating solution for forming a photocatalyst layer, and a photocatalyst-supporting structure.
Background technology:
Conventionally, a photocatalyst carrying structure in which a photocatalyst is carried on a carrier for the purpose of antibacterial, antifungal and decomposition of harmful substances by the action of the photocatalyst is known. Such a photocatalyst-supporting structure is usually produced by forming a photocatalyst layer by applying and curing a photocatalyst layer-forming coating solution containing a photocatalyst component on the surface of a carrier.
The coating solution for forming the photocatalyst layer contains a binder component because it is difficult to fix the photocatalyst layer with a sufficient strength to various carriers using only a photocatalyst component made of a metal oxide such as titanium dioxide. Silica sol has often been used as a binder that can withstand oxidation.
Further, a member (hereinafter referred to as “photocatalyst carrying structure”) in which a film or layer containing a photocatalyst (hereinafter referred to as “photocatalyst layer”) is formed on the surface of the carrier (base material or substrate) is used outdoors. If you do, you will be exposed to wind and rain for a long time. At this time, when the photocatalyst film layer is inferior in water resistance, the photocatalyst film layer is partially or entirely peeled off from the carrier and cannot exhibit sufficient photocatalytic activity. Therefore, when the photocatalyst carrying structure is used outdoors for a longer period of time, it has been desired that the water resistance is higher.
Furthermore, it is known that when the photocatalyst layer is exposed to wind and rain for a long period of time, its transparency deteriorates. Therefore, when a photocatalytic film layer is formed on a transparent carrier such as glass or transparent plastic, it is particularly required to have excellent water resistance and little change in transparency in order to make use of the lower color and pattern. It had been.
An example in which spherical colloidal silica bonded to an elongated shape used in the present invention is used is described as an agricultural material containing a photocatalyst in, for example, Japanese Patent Application Laid-Open No. 11-10803. Are not specifically described in the examples.
Disclosure of the invention:
As a method for evaluating water resistance and long-term durability, a boiling water test as defined in JISK5400 and JISK6744 is known, but even when immersed for 1 hour, there is no peeling and almost no change in transparency. No photocatalytic catalyst layer has been known so far.
The issues that must be solved by the photocatalyst carrier when used in outdoor environments that are exposed to wind and rain for a long period of time are as follows: 1) Even after being immersed in boiling water for 1 hour, the adhesion between the photocatalyst and the carrier It is good and the change in the transparency of the photocatalyst coating is not large. 2) The photocatalytic activity is not greatly reduced by being supported on the support. 3) The support and adhesion by the photocatalyst supported by ultraviolet irradiation outdoors. There are three points that the seat does not deteriorate and that the adhesive strength is maintained and the durability is maintained over a long period of time.
The present invention provides a structure carrying a photocatalyst that can be used for water purification, deodorization, antifouling, sterilization, wastewater treatment, algal growth suppression, and various chemical reactions, and that can solve the above three problems. With the goal.
As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using silica sol having aluminum and zirconium as main components and having a special shape as a binder component, thereby completing the present invention. It came to do. That is, the present invention
(1) A photocatalyst composite containing a photocatalyst and colloidal silica particles, wherein the colloidal silica particles are colloidal silica particles in which spherical colloidal silica particles are bonded in an elongated shape, and a zirconium compound and aluminum are further added to the photocatalyst composite. A photocatalyst complex comprising at least one selected from the group consisting of compounds;
(2) The photocatalyst complex according to (1), further containing a silicon compound,
(3) The photocatalyst complex according to (1) or (2), wherein the spherical colloidal silica particles have a particle size of 10 to 50 nm,
(4) The length of the colloidal silica particles in which the spherical colloidal silica particles are bonded in an elongated shape is in the range of 50 to 400 nm, the photocatalyst complex according to any one of (1) to (3),
(5) Colloidal silica particles in which spherical colloidal silica particles are bonded in an elongated shape have a ratio D1 / D2 of 5 or more measured particle diameter (D1 nm) measured by dynamic light scattering method and measured particle diameter (D2 nm) measured by nitrogen gas adsorption method The D1 is an amorphous colloidal silica particle having an elongated shape having a uniform thickness within a range of 5 to 20 nm by electron microscope observation and having an extension only in one plane by electron microscope observation. The photocatalyst complex according to (1) or (2),
(6) The zirconium compound is selected from the group consisting of zirconium oxide, oxide hydroxide, hydroxide, oxynitrate, oxycarbonate, alkoxide having 1 to 4 carbon atoms, and hydrolyzate of the alkoxide. The photocatalyst complex according to any one of (1) to (5), which is one kind or a mixture of two or more kinds,
(7) The aluminum compound is selected from the group consisting of aluminum oxide, oxide hydroxide, hydroxide, oxynitrate, oxycarbonate, alkoxide having 1 to 4 carbon atoms, and hydrolyzate of the alkoxide. The photocatalyst complex according to any one of (1) to (6), which is one type or a mixture of two or more types,
(8) The zirconium compound or aluminum compound has a specific surface area of 100 m after drying at 150 ° C.2/ Photocatalyst complex according to (6) or (7), wherein the photocatalyst complex is a porous gel of / g or more,
(9) The total amount of the photocatalyst complex is 5 to 50% by weight of the colloidal silica particles and 5 to 60% by weight of the photocatalyst in terms of oxides. 8) The photocatalyst complex according to any one of
(10) The photocatalyst complex according to any one of (1) to (9), which contains 5 to 40% by weight of a zirconium compound in terms of an oxide with respect to the entire photocatalyst complex. ,
(11) The photocatalyst complex according to any one of (1) to (10), wherein the photocatalyst complex contains an aluminum compound in an amount of 20 to 90% by weight in terms of an oxide. .
Also,
(12) A coating solution for forming a photocatalyst layer, comprising a silica sol in which colloidal silica particles in which spherical colloidal silica particles are bound in an elongated shape are dispersed, and photocatalyst particles and / or sol, and further comprising a zirconium compound and an aluminum compound. A photocatalyst layer coating solution comprising at least one selected from the group consisting of:
(13) The photocatalyst layer coating solution according to (12), further comprising polysiloxane,
(14) 0.5 to 5% by weight of a silica sol silica sol in which colloidal silica particles in which spherical colloidal silica particles are bonded in an elongated shape are dispersed in terms of oxide as a solid content with respect to the entire coating liquid for forming a photocatalyst layer, and The photocatalyst particles and / or the sol is contained as a solid content in an amount of 0.5 to 6% by weight (12) or
The coating solution for forming a photocatalyst layer according to (13),
(15) At least one selected from the group consisting of 0.5 to 5% by weight of a zirconium compound and 2 to 9% by weight of an aluminum compound in terms of oxide as a solid content with respect to the entire coating liquid for forming a photocatalyst layer. (12) or (14), a coating solution for forming a photocatalyst layer,
(16) The photocatalyst-forming coating solution according to any one of (12) to (15), wherein the spherical colloidal silica particles have a particle size of 10 to 50 nm.
(17) The coating solution for forming a photocatalyst according to any one of (12) to (16), wherein the length of the colloidal silica particles in which the spherical colloidal silica particles are bonded in an elongated shape is in the range of 50 to 400 nm. ,
(18) The ratio D1 / D2 of the colloidal silica particles in which the spherical colloidal silica particles are combined in an elongated shape is 5 or more by the measurement particle diameter (D1 nm) by the dynamic light scattering method and the measurement particle diameter (D2 nm) by the nitrogen gas adsorption method The D1 is an amorphous colloidal silica particle having an elongated shape having a uniform thickness within a range of 5 to 20 nm by electron microscope observation and having an extension only in one plane by electron microscope observation. (12) The coating solution for forming a photocatalyst according to any one of (12) to (15),
(19) The zirconium compound is selected from the group consisting of zirconium oxide, oxide hydroxide, hydroxide, oxynitrate, oxycarbonate, alkoxide having 1 to 4 carbon atoms, and hydrolyzate of the alkoxide. The coating solution for forming a photocatalyst according to any one of (12) to (18), which is a sol of one kind or a mixture of two or more kinds,
(20) The aluminum compound is selected from the group consisting of an oxide of aluminum, an oxide hydroxide, a hydroxide, an oxynitrate, an oxycarbonate, an alkoxide having 1 to 4 carbon atoms, and a hydrolyzate of the alkoxide. The coating solution for forming a photocatalyst according to any one of (12) to (19), which is a sol of one kind or a mixture of two or more kinds,
(21) The photocatalyst layer forming coating solution according to any one of (12) to (20), wherein the aluminum compound has an average particle size of 2 to 50 nm,
(22) The photocatalyst layer forming coating solution according to any one of (12) to (20), wherein the average particle size of the aluminum compound is 2 to 20 nm.
(23) A photocatalyst layer-supporting structure in which an adhesive layer is formed on the surface of a carrier and a photocatalyst layer is further formed on the surface of the adhesive layer, wherein the photocatalyst layer is any one of (1) to (11) A photocatalyst layer-supporting structure comprising the photocatalyst composite according to claim 1,
(24) The photocatalyst-supporting structure according to (23), wherein the turbidity of the coating film formed by combining the adhesive layer and the photocatalyst layer is 3% or less,
(25) The adhesiveness according to the cross-cut tape method specified in JISK5400 after boiling in boiling ion-exchanged water for 1 hour is an evaluation score of 6 or more, (23) or (24) Photocatalyst carrying structure,
(26) The photocatalyst-supporting structure according to (23), wherein the turbidity of the coating film including the adhesive layer and the photocatalyst layer after boiling for 1 hour in boiling ion-exchanged water is 3% or less,
(27) UV intensity 3 mW / cm2The adherence by the cross-cut tape method defined in JISK5400 after irradiating the light of the black light for 500 hours at a temperature of 40 ° C. and a relative humidity of 90% is an evaluation score of 6 points or more. (23) The photocatalyst carrying structure according to
(28) UV intensity 3 mW / cm2The turbidity of the coating film comprising the adhesive layer and the photocatalyst layer after being irradiated with the light of the black light for 500 hours at a temperature of 40 ° C. and a relative humidity of 90% is 3% or less ( The photocatalyst carrying structure according to 23).
The photocatalyst composite of the present invention basically contains colloidal silica particles in which photocatalyst components and spherical colloidal silica particles are bonded in an elongated shape, and further contains at least one selected from the group consisting of zirconium compounds and aluminum compounds. It is characterized by.
Any photocatalyst can be used as long as it is fixed to the adhesive layer when dried / cured and exhibits photocatalytic activity, such as powder, sol, and solution. In particular, when using a sol-like material having an average particle size of 50 nm or less, preferably 20 nm or less, the transparency of the photocatalyst layer is improved and the linear transmittance is increased. It is preferable when applying to a molded object.
Further, in the case where a color or pattern is printed on the base carrier, such a transparent photocatalyst layer does not impair the base color or pattern. If it is 50 nm or more, the linear transmittance decreases and the haze ratio increases. Here, the haze ratio is a value obtained by a relational expression of haze ratio = (total light transmittance−linear transmittance) / total light transmittance. For example, the window glass of a toilet has a high total light transmittance so that the inside of the toilet is bright, and the haze ratio needs to be high because the inside should not be clearly seen.
Specifically, the photocatalyst is TiO.2, ZnO, SrTiO3, CdS, GaP, InP, GaAs, BaTiO3, KNbO3, Fe2O3, Ta2O5, WO3, SnO2, Bi2O3, NiO, Cu2O, SiC, SiO2, MoS2, InPb, RuO2, CeO2In addition, these photocatalysts include Pt, Rh, RuO.2, Nb, Cu, Sn, Ni, Fe, or other metals or metal oxides can be used. Of these, titanium oxide (TiO2) is considered in view of durability, cost, and photocatalytic activity.2) Is particularly preferable, and anatase-type titanium oxide is more preferable in consideration of photocatalytic activity. Further, not only titanium oxide that exhibits catalytic activity with light containing a large amount of ultraviolet rays such as sunlight, but also titanium oxide that exhibits catalytic activity in indoor light with little ultraviolet rays by doping a noble metal or the like can be used.
The content of the photocatalyst in the photocatalyst complex is preferably 5% by weight to 60% by weight in terms of oxide with respect to the entire photocatalyst complex. If it is less than 5% by weight, the photocatalytic activity is remarkably lowered. On the other hand, when it exceeds 60% by weight, the photocatalytic activity becomes high, but the adhesiveness with the adhesive layer becomes poor.
The colloidal silica particles used in the present invention are characterized by colloidal silica particles in which spherical colloidal silica particles are bonded in an elongated shape. As a specific example of the shape, when the spherical colloidal silica particles are found in the pearl of a pearl necklace, A shape like a part of a pearl necklace can be illustrated. That is, a particle in which 3 or more, preferably 5 or more, more preferably 7 or more spherical silica particles are connected can be exemplified. In addition, the shape of each spherical colloidal particle need not be clear, and it may be partially elongated in a cylindrical shape, and the spherical colloidal particles need to be bonded. Rather, it is preferable that the whole particle has an elongated shape.
In the elongated shape, the length is preferably in the range of 50 to 400 nm, the thickness is preferably in the range of 10 to 50 nm, and the thickness is preferably uniform throughout. Furthermore, the elongated shape preferably extends in a two-dimensional direction starting from a certain spherical colloidal silica particle. Moreover, as long as it has an elongated shape as a whole, it may have a somewhat branched structure.
When the spherical colloidal silica particles are bonded in a necklace shape as described above, the average particle diameter of the spherical colloidal silica particles is preferably in the range of 10 to 50 nm.
Specifically, as the colloidal silica particles having the above-described characteristics, the ratio D1 / D2 of the measured particle diameter (D1 nm) by the dynamic light scattering method and the measured particle diameter (D2 nm) by the nitrogen gas adsorption method is 5 or more. The D1 is 40 to 300 nm, and exemplifies elongated amorphous colloidal silica particles having a uniform thickness in the range of 5 to 20 nm by electron microscopy and having an extension in only one plane. be able to. Examples of a method for producing such a sol in which colloidal silica particles are dispersed include the methods described in JP-A-1-317115 and JP-A-7-118008.
The zirconium compound used in the present invention is added for the purpose of improving the alkali resistance of the photocatalyst complex. Examples of the zirconium compound include zirconium oxide, oxide hydroxide, hydroxide, nitrate, oxynitrate, carbonate, oxycarbonate, oxalate, oxysuccinate, acetate, oxyacetate, carbon number 1 to A gel of one or a mixture of two or more selected from the group consisting of 6 alkoxides and hydrolysis products of the alkoxides is preferred.
Preferred examples of the zirconium compound include zirconium oxide, zirconium oxynitrate, zirconium oxychloride, hydrated zirconium oxide, zirconium oxyhydroxide, hydrated zirconium nitrate, hydrated zirconium oxychloride, zirconium oxalate, zirconium acetate, zirconium tetra Mention may be made of isopropoxide, zirconium tetrabutoxide, zirconium dibutoxide acetylacetonate, zirconium dibutoxide lactate, hydrolysis products of zirconium butoxide, and hydrolysis products of zirconium isopropoxide.
The aluminum compound is added for the purpose of further improving the alkali resistance of the photocatalyst complex and lowering the haze ratio. Examples of the aluminum compound include aluminum oxide, oxide hydroxide, hydroxide, nitrate, oxynitrate, carbonate, oxycarbonate, oxalate, oxysuccinate, acetate, oxyacetate, and 1 to 6 carbon atoms. 1 type, or 2 or more types of mixtures chosen from the group which consists of a alkoxide of this, and the hydrolysis product of this alkoxide is preferable.
Preferred specific examples of aluminum compounds include aluminum oxide, aluminum oxide hydroxide, aluminum hydroxide, hydrated aluminum oxide, boehmite, aluminum nitrate, aluminum oxynitrate, aluminum carbonate, aluminum oxycarbonate, aluminum oxalate, aluminum oxyoxalate, and acetic acid. Examples thereof include aluminum, aluminum oxyacetate, aluminum triisopropoxide, aluminum tributoxide, aluminum butoxide acetylacetonate, aluminum butoxide lactate, a hydrolysis product of aluminum butoxide, a hydrolysis product of aluminum isopropoxide, and the like.
The zirconium compound or aluminum compound used together with the photocatalyst is preferably a sol having an average particle diameter of 2 nm to 50 nm, preferably 2 nm to 20 nm. When using a particle having such a particle size, the transparency of the photocatalyst layer is improved and the linear transmittance is increased. Therefore, particularly when applied to a glass substrate or plastic molded product that requires transparency. preferable. Further, in the case where a color or pattern is printed on the base carrier, such a transparent photocatalyst layer does not impair the base color or pattern. Moreover, when using a thing with an average particle diameter of 50 nm or more, a linear transmittance | permeability reduces and a haze rate becomes high.
Zirconium or aluminum oxide, oxide hydroxide, hydroxide in the photocatalyst composite has a specific surface area of 100 m after drying at 150 ° C.2It is preferable to use a porous gel of at least / g. The porous gel has adsorptivity and has an effect of enhancing photocatalytic activity.
The content of the zirconium compound in the photocatalyst complex is preferably 5 to 40% by weight in terms of oxide with respect to the entire photocatalyst complex. If it is less than 5% by weight, the alkali resistance of the photocatalyst layer becomes poor. On the other hand, if it exceeds 40% by weight, the transparency deteriorates.
The content of the aluminum compound in the photocatalyst complex is preferably 20 to 90% by weight in terms of oxide with respect to the entire photocatalyst complex. If it is less than 20% by weight, the effect of suppressing the increase in the haze ratio of the photocatalyst layer and the effect of increasing the alkali resistance are poor. On the other hand, when the addition amount exceeds 90% by weight, the photocatalytic activity decreases.
The total content of the zirconium compound and the aluminum compound in the photocatalyst complex is preferably 40 to 95% by weight in terms of these acid compounds. If it is less than 40% by weight, the adhesion to the adhesive layer becomes insufficient, and if it exceeds 95% by weight, the amount of photocatalyst that can be added is reduced, so that the photocatalytic activity is significantly lowered.
The film strength is improved by further containing a silicon compound in the photocatalyst complex. As a silicon compound,
SiCln1(OH) n2R1n3(OR2) N4
Or a hydrolysis product thereof.
Where R1Is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl, octyl, aminomethyl, aminoethyl, carboxymethyl, carboxyethyl, chloromethyl, chloroethyl, chloropropyl groups, etc. (amino group, carboxyl An alkyl group having 1 to 8 carbon atoms, which may be substituted with a group or a chlorine atom.
R2Is an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl group, or methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, An alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group such as methoxyethyl, ethoxymethyl, propoxyethyl, methoxypropyl, or methoxybutyl group. N1, N2And n3Represents 0, 1 or 2, n4Represents an integer from 2 to 4 and n1+ N2+ N3+ N4= 4.
Preferable specific examples of the silicon alkoxide represented by the above formula include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and the like.
The content of the silicon compound in the photocatalyst complex is preferably 1 to 20% by weight in terms of oxide with respect to the entire photocatalyst complex.
These multicomponents may further contain tin, niobium, tantalum oxides, or their hydroxides for the purpose of improving the coating strength. In that case, if the content of aluminum oxide, oxide hydroxide or hydroxide in the photocatalyst layer is within the range of the content to be added to improve the alkali resistance, extremely excellent alkali resistance Can indicate
The coating solution for forming a photocatalyst layer of the present invention contains a silica sol in which colloidal silica particles in which spherical colloidal silica particles are bonded in an elongated shape is dispersed, and a photocatalyst particle and / or sol, and further comprises a group consisting of a zirconium compound and an aluminum compound. It contains at least one selected from
Specific examples of the silica sol, the zirconium compound, the aluminum compound, and the photocatalyst in which the colloidal silica particles in which the spherical colloidal silica particles are combined in an elongated shape are contained in the coating solution for forming the photocatalyst layer include colloidal contained in the photocatalyst complex. The thing similar to what was listed as a preferable thing of a silica particle, a zirconium compound, an aluminum compound, and a photocatalyst can be used.
The zirconium compound, aluminum compound and photocatalyst are preferably used in the form of a sol. When a sol is used, an acid or alkali peptizer can be added to the photocatalyst coating solution for stabilization. In addition, in order to improve adhesion and operability, 5% by weight or less of a surfactant or the like can be added to the sol suspension.
The amount of each component contained in the coating liquid for forming the photocatalyst layer is 0% of the silica sol silica sol in which the colloidal silica particles in which the spherical colloidal silica particles are bonded in an elongated shape are dispersed as an oxide as a solid content with respect to the entire coating liquid. 0.5 to 5% by weight, and photocatalyst particles and / or sol is preferably 0.5 to 6% by weight as a solid content, with respect to the entire photocatalyst layer forming coating liquid, in terms of oxide as a solid content, It is preferable that the zirconium compound is 0.5 to 5% by weight and the aluminum compound is 2 to 9% by weight.
When the silicon compound is contained in the photocatalyst complex, it is preferable to contain 0.001 to 5% by weight of the silicon compound in terms of oxide as a solid content with respect to the entire coating solution for forming the photocatalyst layer. As the silicon compound, for example, a hydrolyzate of silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or the hydrolyzate product is preferable. When the number of carbon atoms of the alkoxy group of the silicon alkoxide exceeds 6, the hydrolysis rate becomes very slow. Polysiloxane obtained by hydrolyzing silicon alkoxide partially containing chlorine can also be used. However, when polysiloxane containing a large amount of chlorine is used, the carrier is corroded by chlorine ions as impurities. Or the adhesiveness may decrease.
As such a silicon alkoxide, for example, a compound represented by the following formula can be preferably used.
SiCln1(OH) n2R1n3(OR2) N4
Where R1Is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl, octyl, aminomethyl, aminoethyl, carboxymethyl, carboxyethyl, chloromethyl, chloroethyl, chloropropyl groups, etc. (amino group, carboxyl An alkyl group having 1 to 8 carbon atoms, which may be substituted with a group or a chlorine atom.
R2Is an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl group, or methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, An alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group such as methoxyethyl, ethoxymethyl, propoxyethyl, methoxypropyl, or methoxybutyl group. N1, N2And n3Represents 0, 1 or 2, n4Represents an integer from 2 to 4 and n1+ N2+ N3+ N4= 4.
Preferable specific examples of the silicon alkoxide represented by the above formula include Si (OCH3)4, Si (OC2H5)4, Si (OC3H7)4, Si (OC4H9)4, Si (OC5H11)4, Si (OC6H13)4, SiCH3(OCH3)3, SiCH3(OC2H5)3, SiCH3(OC3H7)3, SiCH3(OC3H7)3, SiCH3(OC4H9)3SiCl (OCH3)3, SiCl (OC2H5)3, SiCl (OC3H7)3, SiCl (OC4H9)3, SiCl (OC6H13)3, SiCl (OH) (OCH3)2, SiCl (OH) (OC2H5)2, SiCl (OH) (OC3H7)2, SiCl (OH) (OC4H9)2, SiCl2(OCH3)2, SiCl2(OC2H5)2Etc.
As a method for preparing a coating solution for forming a photocatalyst layer, (a) a method of mixing an oxide of zirconium or aluminum, a sol solution of oxide hydroxide or hydroxide, a photocatalyst, a colloidal silica sol, etc., an oxide of zirconium or aluminum , A method of mixing a photocatalyst with colloidal silica sol or the like in the state of a precursor solution of oxide hydroxide or hydroxide sol, (b) zirconium or aluminum oxide, oxide hydroxide or hydroxide sol solution, and Any method can be adopted as long as it is a method in which the colloidal silica sol is mixed uniformly in the photocatalyst layer, such as a method of mixing a sol or solution for forming a photocatalyst. In addition, (c) photocatalyst particles or sol, colloidal silica sol, etc. are dispersed in a precursor solution of zirconium or aluminum oxide, oxide hydroxide or hydroxide sol, and hydrolysis or neutralization decomposition during coating And can be made into a sol.
Examples of the solvent used include alcohols such as water, methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol and t-butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and cyclohexanone, diethyl ether, methyl Cellsolve, ethers such as tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane and chloroform, esters such as saxane ethyl, propyl acetate, butyl acetate, pentane, hexane, cyclohexane, etc. Of saturated hydrocarbons. Moreover, these 2 types or more can also be mixed and used. Of these, water-alcohol solvents are particularly preferred.
The structure carrying the photocatalyst according to the present invention has a structure in which an adhesive layer is provided between the photocatalyst layer and the carrier. The adhesive layer provided between the photocatalyst layer and the carrier has the effect of protecting the underlying carrier from deterioration due to photocatalysis and the effect of firmly adhering the photocatalyst layer to the carrier, and the adhesive layer itself is photocatalytic. It is characterized by being less susceptible to deterioration due to.
The carrier is not particularly limited as long as it can carry a photocatalyst through an adhesive layer. For example, it is possible to obtain a structure provided with this adhesive layer and photocatalyst layer even if the ceramic, inorganic material, carrier material is an organic polymer that cannot be heated, or a metal that is easily oxidized and corroded by heat, water, or the like. it can. Further, as the carrier shape, any complicated shape such as a film shape, a sheet shape, a plate shape, a tubular shape, a fiber shape, and a net shape can be used. The thickness of the carrier is preferably 10 μm or more because it can be firmly supported. Furthermore, in order to improve the adhesion between the carrier and the adhesive layer, a carrier whose surface has been subjected to easy adhesion treatment such as discharge treatment or primer treatment can be used.
The material of the adhesive layer is not particularly limited as long as it can protect the carrier from deterioration due to photocatalysis and can firmly fix the photocatalyst layer. Specifically, (1) the silicon content is converted into oxide. 2 to 10% by weight of a silicon-modified resin such as (acrylic silicone resin, epoxy silicone resin, polyester silicone resin), (2) a resin containing 3 to 90% by weight of polysiloxane in terms of oxide, or (3 ) A resin containing 5 to 90% by weight of colloidal silica in terms of oxide can be used. These resins are suitable for firmly bonding the photocatalyst and protecting the carrier from the photocatalyst.
Silicon-modified resins such as acrylic silicon resins with a silicon content of less than 2% by weight in terms of oxides, resins with a polysiloxane content of less than 3% by weight in terms of oxides, and colloidal silica content in oxides If converted to less than 5% by weight of resin, adhesion to the photocatalyst layer becomes poor. Further, the adhesive layer is deteriorated by the photocatalyst, and the photocatalyst layer is easily peeled off. Silicon-modified resin such as acrylic-silicone resin whose silicon content is more than 10% by weight in terms of oxide, resin whose polysiloxane content is more than 90% by weight in terms of oxide, colloidal silica content is oxide If the resin exceeds 90% by weight, the adhesion to the carrier is lowered.
Examples of the resin into which silicon is introduced include acrylic resin, epoxy resin, polyester resin, alkyd resin, and urethane resin. Among these, acrylic resins, epoxy resins, and polyester resins are particularly preferable in terms of film formability, toughness, and adhesion to the carrier. These resins can be used in either a solution form or an emulsion type. Moreover, additives, such as a crosslinking agent, may be contained.
When the polysiloxane contained in the resin of the adhesive layer is a hydrolyzate of silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or the hydrolyzate product, the support having improved adhesion and durability A structure can be obtained. When the number of carbon atoms of the alkoxy group of the silicon alkoxide exceeds 6, the hydrolysis rate is very slow, making it difficult to cure in the resin, resulting in poor adhesion and durability. Polysiloxane obtained by hydrolyzing silicon alkoxide partially containing chlorine can also be used. However, when polysiloxane containing a large amount of chlorine is used, the carrier is corroded by chlorine ions as impurities. Or the adhesiveness may decrease.
As such a silicon alkoxide, for example, a compound represented by the following formula can be preferably used.
SiCln1(OH) n2R1n3(OR2) N4
Where R1Is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl, octyl, aminomethyl, aminoethyl, carboxymethyl, carboxyethyl, chloromethyl, chloroethyl, chloropropyl groups, etc. (amino group, carboxyl An alkyl group having 1 to 8 carbon atoms, which may be substituted with a group or a chlorine atom.
R2Is an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl group, or methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, An alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group such as methoxyethyl, ethoxymethyl, propoxyethyl, methoxypropyl, or methoxybutyl group. N1, N2And n3Represents 0, 1 or 2, n4Represents an integer from 2 to 4 and n1+ N2+ N3+ N4= 4.
Preferable specific examples of the silicon alkoxide represented by the above formula include Si (OCH3)4, Si (OC2H5)4, Si (OC3H7)4, Si (OC4H9)4, Si (OC5H11)4, Si (OC6H13)4, SiCH3(OCH3)3, SiCH3(OC2H5)3, SiCH3(OC3H7)3, SiCH3(OC3H7)3, SiCH3(OC4H9)3SiCl (OCH3)3, SiCl (OC2H5)3, SiCl (OC3H7)3, SiCl (OC4H9)3, SiCl (OC6H13)3, SiCl (OH) (OCH3)2, SiCl (OH) (OC2H5)2, SiCl (OH) (OC3H7)2, SiCl (OH) (OC4H9)2, SiCl2(OCH3)2, SiCl2(OC2H5)2Etc.
There are various methods for introducing silicon of these silicon-modified resins, such as transesterification, grafting reaction using silicon macromers and reactive silicon monomers, hydrosilylation reaction, block copolymerization method, etc. Can also be used.
For example, as a method for introducing polysiloxane into a resin, (1) a method in which silicon alkoxide is mixed with a resin solution in a monomer state and hydrolyzed with moisture in the air when forming an adhesive layer; There are various methods such as mixing the partially hydrolyzed product with the resin and further hydrolyzing with moisture in the air when forming the adhesive layer. Any method can be used as long as it can be mixed with the resin uniformly.
Further, in order to adjust the hydrolysis rate of silicon alkoxide, a small amount of acid or base catalyst may be added. The amount of polysiloxane added to the resin is preferably 3 to 90% by weight in terms of oxide in order to firmly adhere the photocatalyst layer to the carrier.
Any resin such as an acrylic resin, an epoxy resin, a polyester resin, a urethane resin, or an alkyd resin can be used as the resin into which polysiloxane is introduced. Among these, an acrylic resin, an epoxy resin, a polyester resin, or a mixed resin thereof is preferable in terms of durability and alkali resistance when a silicon-modified resin is used.
When the adhesive layer contains colloidal silica, the particle diameter of the colloidal silica is preferably 10 nm or less. When the particle diameter is 10 nm or more, the resin in the adhesive layer is not only easily deteriorated by the photocatalyst but also the adhesion between the photocatalyst layer and the adhesive layer is deteriorated.
The simplest method for introducing colloidal silica into the resin is to form a protective film by mixing a resin solution and a colloidal silica solution, followed by coating and drying. In addition, a polymer obtained by polymerizing a resin in a state where colloidal silica is dispersed can also be used.
Moreover, in order to improve the adhesiveness and dispersibility of colloidal silica and resin, colloidal silica treated with a silane coupling agent can also be used.
The amount of colloidal silica added to the resin is preferably 5 to 90% by weight in terms of oxide in order to firmly adhere the photocatalytic layer to the support.
Any resin such as an acrylic resin, an epoxy resin, a urethane resin, a polyester resin, or an alkyd resin can be used as a resin for introducing colloidal silica. Among these resins, acrylic resins, epoxy resins, and polyester resins are particularly preferable because when they are silicon-modified resins, those having excellent durability and alkali resistance can be obtained.
Colloidal silica may be any silica sol obtained by cation exchange of an aqueous sodium silicate solution or silica sol obtained by hydrolyzing silicon alkoxide.
Furthermore, in the present invention, a resin containing both polysiloxane and colloidal silica can be used as the adhesive layer. In that case, if the total content of the polysiloxane and colloidal silica in the adhesive layer is within the range of the content showing the improvement in alkali resistance in terms of oxide, the same excellent alkali resistance will be exhibited. be able to
When the resin used for the adhesive layer is a resin containing colloidal silica or a resin containing polysiloxane, the particle diameter of the colloidal silica or polysiloxane is preferably 10 nm or less. If the particle diameter of colloidal silica or polysiloxane exceeds 10 nm, the dispersibility deteriorates and the translucency of the adhesive layer decreases, so the total light transmittance at a total wavelength of 550 nm of the adhesive layer and the photocatalyst layer is 70. % Or less.
In addition, a light stabilizer and / or an ultraviolet absorber can be further added to the adhesive layer resin for the purpose of suppressing deterioration due to photocatalytic action. As the light stabilizer that can be used, a hindered amine system is preferable, but other substances can also be used. As the ultraviolet absorber, triazole or the like can be used. These addition amounts are 0.005 weight%-10 weight% with respect to resin, Preferably they are 0.01 weight%-5 weight%. It is also preferable to improve the adhesion with the photocatalyst layer by treating the adhesive layer with a silane or titanium coupling agent.
Examples of the method for forming the adhesive layer on the carrier include a method in which an adhesive resin solution is coated, dried and cured by a printing method, a sheet molding method, a spray spraying method, a dip coating method, a spin coating method, and the like. . Although drying temperature changes with kinds of solvent and resin, generally about 50 to 300 degreeC is preferable.
The thickness of the adhesive layer is preferably about 0.1 μm to 20 μm in order to obtain good adhesion with the photocatalyst layer. When the thickness of the adhesive layer is 0.1 μm or less, the function of firmly bonding the photocatalytic layer is weakened. On the other hand, there is no particular problem when the thickness is 20 μm or more, but there are few merits to make it 20 μm or more in consideration of actual coating.
The photocatalyst layer can be formed by coating the coating solution for forming the photocatalyst layer on the surface of the adhesive layer by a printing method, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, etc., and drying and curing. . The preferred temperature during drying and curing varies depending on the carrier material and the resin material in the adhesive layer, but is usually about 50 ° C to 300 ° C.
The photocatalytic activity is higher when the photocatalytic layer is thicker, but if it exceeds 20 μm, the photocatalytic activity is saturated, but it is often difficult in actual coating processing, and the light transmittance of the photocatalytic layer is reduced. 20 μm or less is preferable. On the other hand, when the thickness of the photocatalyst is less than 0.1 μm, the translucency is improved, but the ultraviolet ray used by the photocatalyst is also transmitted, so that high activity cannot be expected.
The total wavelength of the photocatalyst layer and the adhesive layer is 550 nm by using photocatalyst particles having a thickness of 0.1 μm or more and 20 μm or less and an average particle size of 50 nm or less and an aluminum oxide or hydroxide gel. Can have a total light transmittance of 80% or more and a haze ratio of 2% or less. Such a photocatalyst-supporting structure can be used for illumination of transmitted visible light when a transparent carrier is used, and even if the carrier is opaque, the handle on the carrier is not damaged, so that it has excellent decorativeness. It becomes.
The photocatalyst-supporting structure of the present invention thus obtained is characterized in that the turbidity of the coating film formed by combining the adhesive layer and the photocatalyst layer is 3% or less. In this case, turbidity is used in the same meaning as the haze rate described above.
Furthermore, the adhesiveness by the cross-cut tape method defined in JISK5400 after boiling for 1 hour in boiling ion-exchanged water is 6 or more evaluation points. Further, the turbidity of the coating film including the adhesive layer and the photocatalyst layer after boiling in boiling ion exchange water for 1 hour is 3% or less, and the ultraviolet intensity is 3 mW / cm.2The adhesion by the cross-cut tape method defined in JISK5400 after irradiating the light of the black light for 500 hours at a temperature of 40 ° C. and a relative humidity of 90% is characterized by an evaluation score of 6 points or more, UV intensity 3mW / cm2The turbidity of the coating film including the adhesive layer and the photocatalyst layer after being irradiated with the light of the black light for 500 hours at a temperature of 40 ° C. and a relative humidity of 90% is 3% or less.
The structure carrying the photocatalyst of the present invention includes architectural paints, wallpaper, window glass, blinds, curtains, carpets, lighting fixtures, lighting lights, road lights, tunnel lighting lights, highway and Shinkansen sound insulation walls, black lights, ship bottoms. -Can be used for fishing net antifouling paints, water treatment fillers, agricultural bi-films, grass protection sheets, packaging materials, etc. In particular, when used in a hot and humid environment or an outdoor environment, it exhibits excellent durability and transparency.
Best Mode for Carrying Out the Invention:
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to an Example.
1) Photocatalyst layer forming coating solution
(1) Photocatalyst
The following photocatalyst catalysts were used.
(T-1) Nitric acid acidic titanium oxide sol (crystal particle diameter: 8 nm)
(2) Silica sol
The following silica sol was used.
(S-1) Necklace-like colloidal silica (Nissan Chemical Snowtex PS)
(3) Aluminum compound
The following aluminum compounds were used.
(A-1) Aluminum oxide hydroxide (boehmite) fine particles (Aluminum sol 10 manufactured by Kawaken Fine Chemicals)
(4) Zirconium compound
The following zirconium compounds were used.
(Z-1) Wako Pure Chemicals reagent special grade zirconium oxynitrate hexahydrate dissolved in water to make a 10% aqueous solution, then heated for 12 hours to distill off half of the water at normal pressure Was used as the zirconium oxynitrate solution.
(5) Preparation of coating solution for forming photocatalyst layer
The above-mentioned titanium oxide photocatalyst, sol solution and compound solution were prepared in an appropriate range of pH 1.5 to 9, mixed, and a predetermined amount of surfactant was added to obtain a coating solution for forming a photocatalyst layer.
2) Production of photocatalyst carrying structure
(1) Carrier
(TA) Soda lime glass plate
(TB) Transparent acrylic board
(TC) Aluminum plate
(2) Adhesive layer The polysiloxane contained in the adhesive layer was as follows.
(PS-1) Shin-Etsu Chemical Silicon Tetramethoxide Monomer
(PS-2) Colcoat polymethoxysiloxane trade name methyl silicate 51
(PS-3) Colcoat polyethoxysiloxane product name The following were used as colloidal silica contained in the ethyl silicate 40 adhesive layer.
(KS-1) Catalytic Chemical Co., Ltd. product name Cataloid SI-350, particle size 7-9 nm
(KS-2) Nissan Chemical Co., Ltd. product name Snowtex ST-XS, particle size 4-6 nm Polysiloxane or colloidal silica was introduced as the resin solution below. The silicon content is the SiO in the resin solids.2Converted to and displayed.
(J-1) Acrylic-silicone resin xylene solution having a silicon content of 3% by weight
(J-2) Xylene isopropanol solution of acrylic-silicon resin having a silicon content of 10% by weight
(J-3) Acrylic-silicone emulsion resin aqueous solution having a silicon content of 3% by weight
(J-4) Epoxy-silicon resin methyl ethyl ketone solution having a silicon content of 3% by weight
(J-5) Polyester-silicon resin ethyl acetate solution having a silicon content of 3% by weight
(J-6) Acrylic emulsion resin aqueous solution
Polysiloxane or colloidal silica was mixed with the resin solution and the concentration was adjusted to obtain an adhesive layer forming solution. The adhesive layer was formed by a dipping method when the thickness was 2 μm or less or when the carrier shape was other than a flat plate, and by a Baker applicator when the carrier was a flat plate and the thickness was 2 μm or more. The adhesive layer was dried at 80 ° C. when the carrier material was (TB) and at 120 ° C. otherwise.
(3) The photocatalyst layer is a dipping method when the thickness of the carrier is 2 μm or less or when the shape of the carrier is other than a flat plate. When the carrier is a flat plate and the thickness is 2 μm or more, a back coater is used A coating was formed on the phase surface. The photocatalyst layer was dried at the same temperature as the adhesive layer was dried.
3) Performance test of photocatalyst carrying structure
The following performance test was performed using each sample carrying the photocatalyst obtained above. (1) Photocatalytic activity evaluation test
A sample carrying a photocatalyst cut to a size of 70 mm × 70 mm was placed in a 4 liter Pyrex (registered trademark) glass container. A mixed gas of air and aldehyde was added to the container so that the aldehyde concentration was 200 ppm. Next, the UV intensity of the support sample is 2 mW / cm.2After being irradiated for 3 hours with light from a black light (FL15BLB, manufactured by Toshiba Lighting & Technology), the aldehyde gas concentration inside the container was measured by a gas chromatograph, and the photocatalytic activity was evaluated based on the amount of decrease.
The evaluation criteria are as follows.
Performance evaluation based on decrease in aldehyde gas concentration after 3 hours of irradiation
100ppm or more A
50-100ppm B
20-50ppm C
(2) Adhesion evaluation test
On the surface of the sample carrying the photocatalyst, 25 squares were formed at intervals of 2 mm by cutting, and adhesion was evaluated by a cross-cut tape method test specified in JISK5400. The evaluation score was based on the criteria described in JISK5400.
(3) Boiling water resistance evaluation test
A boiling water resistance test was conducted in accordance with a boiling water resistance test specified in JISK5400. However, the immersion time was 1 hour.
(4) Measurement of haze ratio
Using the carrier before supporting the adhesive layer and the photocatalyst layer as a reference, the total light transmittance at a wavelength of 550 nm and the haze ratio of the supported sample were measured with a self-recording spectrophotometer (U-4000 type manufactured by Hitachi, Ltd.). .
(5) Durability test
UV light intensity of 3mW / cm with black light on sample carrying photocatalyst2After being irradiated for 500 hours in a constant temperature and humidity chamber at a temperature of 40 ° C. and a relative humidity of 90%, the adhesion was measured by a cross-cut tape method specified in JISK5400 to evaluate durability. The evaluation score was the same as the adhesion evaluation.
The following Table 1 summarizes the performance test results of the photocatalyst-supporting structures obtained in Table 2 and the modes of Examples and Comparative Examples in which the types and amounts of the respective materials were changed.
Moreover, the comparative example 3 is a case where there is too much zirconia sol in a photocatalyst layer. High initial haze rate.
Examples 1 to 3 are examples in which an acrylic-silicon resin is used for the adhesive layer and a photocatalyst layer using necklace-shaped colloidal silica is used. These samples were evaluated well by the boiling water resistance test, and the durability was also good.
Examples 4 to 14 are examples in which an acrylic-silicon resin containing polysiloxane was used for the adhesive layer, and a photocatalyst layer using necklace-shaped colloidal silica was used.
Examples 7, 8, and 11 are examples carried on a transparent acrylic plate. These samples also had good durability.
In addition, when the epoxy-silicon resin introduced with polysiloxane (Example 16), the polyester-silicon resin (Example 17), or the acrylic resin (Example 18) is used as the adhesive layer resin, good performance is obtained. Indicated.
In Examples 19 to 26, a resin containing colloidal silica was used for the adhesive layer, and the catalytic activity, boiling water resistance, and durability were good.
Samples obtained in Examples 1 to 26, durability test using black light under high temperature and high humidity, boiling water test, and accelerated light resistance using sunshine carbon arc weather meter (Suga test equipment, WEL-SUN-HCH type) The sample subjected to the property test was again examined for the photocatalytic activity by the amount of acetaldehyde gas decomposed by the same method as in the initial stage. All samples were found to maintain the initial photocatalytic activity.
In Examples 27 to 31, a photocatalyst layer was directly formed on a soda lime glass plate without using an adhesive layer, and then dried at 200 ° C .. The catalytic activity, boiling water resistance, and durability were It was good.
The samples obtained in Examples 27 to 31 were subjected to durability test using a black light under high temperature and high humidity, boiling water test, and accelerated light resistance using a sunshine carbon arc weather meter (Suga test equipment, WEL-SUN-HCH type). The sample which took 2000 hours for the property test was again examined for the photocatalytic activity by the decomposition amount of acetaldehyde gas in the same manner as in the initial stage. It was found that all the samples maintained the initial photocatalytic activity.
When the samples obtained in Examples 27 to 31 were measured for the haze ratio of the samples subjected to an accelerated light resistance test with a sunshine carbon arc weather meter (Suga test equipment, WEL-SUN-HCH type) for 2000 hours, All the values showed values within 2%, and it was found that high transparency was maintained.
Example 32
A film was formed in the same manner as in Example 12 except that polymethoxysiloxane (reagent) was further added to the photocatalyst layer agent so as to be 10% by weight with respect to the total solid content in terms of oxide. The photocatalyst was rated B. However, when a felt abrasion test was performed using a rubbing tester manufactured by Ohira Rika Kogyo Co., Ltd., the coating film of Example 12 was found to be peeled after 200 reciprocations, whereas the coating film of Example 32 was used. No peeling was observed even after 400 reciprocations.
Example 33
A film was formed in the same manner as in Example 14 except that polymethoxysiloxane (reagent) was further added to the photocatalyst layer agent so as to be 20% by weight with respect to the total solid content in terms of oxide. The photocatalyst was rated C. However, when a felt abrasion test was performed using a rubbing tester manufactured by Ohira Rika Kogyo Co., Ltd., the coating film of Example 14 was found to be peeled after 100 reciprocations, whereas Example 33 was 400 reciprocations. However, no peeling was observed.
Industrial applicability:
As described above, the photocatalyst composite of the present invention has very high photocatalytic activity and excellent transparency.
The coating solution for forming a photocatalyst layer of the present invention is excellent in storage stability and can easily form a photocatalyst layer. In addition, since the obtained photocatalyst layer can be transparent so as to transmit visible light, the catalyst can be supported without impairing the handle pattern of the carrier, and the decorativeness is impaired on a wide range of carriers such as general-purpose resins and natural fibers. It is possible to obtain a photocatalyst-supporting structure having excellent activity.
In the photocatalyst carrying structure of the present invention, the photocatalyst is firmly bonded to the carrier, the photocatalytic activity is very high, and the carrier is not deteriorated or the photocatalyst is not detached by the photocatalytic action.
The photocatalyst-supporting structure of the present invention can be used for a long time even under light irradiation. In addition, the evaluation of the alkali resistance test is also good, and high adhesion is maintained even after the accelerated weather resistance test by the sunshine carbon arc weather meter, so it can be used in a hot and humid environment or an outdoor environment. .
Claims (21)
前記ジルコニウム化合物及び前記アルミニウム化合物が、夫々、酸化物、酸化水酸化物、水酸化物、オキシ硝酸塩、オキシ炭酸塩、炭素数１〜４のアルコキシド、及び該アルコキシドの加水分解物からなる群から選ばれる１種または２種以上の混合物であって、１５０℃で乾燥後の比表面積が１００ｍ２／ｇ以上の多孔質ゲルであり、
光触媒複合体全体に対して、酸化物に換算して、ジルコニウム化合物を５〜４０重量％、又は、アルミニウム化合物を２０〜９０重量％含有することを特徴とする光触媒複合体。(A) a photocatalyst, (B) a colloidal silica particle in which spherical colloidal silica particles are bonded in an elongated shape, and (C) a photocatalyst complex containing at least one selected from the group consisting of a zirconium compound and an aluminum compound. ,
The zirconium compound and the aluminum compound are each selected from the group consisting of oxide, oxide hydroxide, hydroxide, oxynitrate, oxycarbonate, alkoxide having 1 to 4 carbon atoms, and hydrolyzate of the alkoxide. A porous gel having a specific surface area of 100 m 2 / g or more after drying at 150 ° C.
A photocatalyst composite comprising 5 to 40% by weight of a zirconium compound or 20 to 90% by weight of an aluminum compound in terms of an oxide with respect to the entire photocatalyst composite.
光触媒層形成用塗布液全体に対して、固形分として酸化物換算で、ジルコニウム化合物を０．５〜５重量％、又は、アルミニウム化合物を２〜９重量％含有し、
前記ジルコニウム化合物及びアルミニウム化合物が、夫々、酸化物、酸化水酸化物、水酸化物、オキシ硝酸塩、オキシ炭酸塩、炭素数１〜４のアルコキシド、及び該アルコキシドの加水分解物からなる群から選ばれる１種または２種以上の混合物のゾルであることを特徴とする光触媒層形成用塗布液。(A ′) at least selected from the group consisting of photocatalyst particles and / or sol, (B ′) silica sol in which colloidal silica particles in which spherical colloidal silica particles are bound in an elongated shape are dispersed, and (C ′) a zirconium compound and an aluminum compound. A coating solution for forming a photocatalyst layer containing one kind,
Containing 0.5 to 5% by weight of a zirconium compound or 2 to 9% by weight of an aluminum compound in terms of oxide as a solid content with respect to the entire coating liquid for forming a photocatalyst layer,
The zirconium compound and the aluminum compound are each selected from the group consisting of an oxide, an oxide hydroxide, a hydroxide, an oxynitrate, an oxycarbonate, an alkoxide having 1 to 4 carbon atoms, and a hydrolyzate of the alkoxide. A coating solution for forming a photocatalyst layer, which is a sol of one kind or a mixture of two or more kinds.
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| JP2003535930A JP4738736B2 (en) | 2001-10-12 | 2002-10-11 | Photocatalyst composite, coating solution for forming photocatalyst layer, and photocatalyst carrying structure |
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| JP4393963B2 (en) * | 2004-03-17 | 2010-01-06 | 住友化学株式会社 | Photocatalyst coating liquid |
| JP4971608B2 (en) * | 2005-08-26 | 2012-07-11 | 日本曹達株式会社 | Photocatalyst carrying structure |
| JP4092714B1 (en) | 2007-03-26 | 2008-05-28 | Ｔｏｔｏ株式会社 | Photocatalyst-coated body and photocatalyst coating liquid therefor |
| US7919425B2 (en) | 2008-03-26 | 2011-04-05 | Toto Ltd. | Photocatalyst-coated body and photocatalytic coating liquid for the same |
| JP4879839B2 (en) * | 2007-08-10 | 2012-02-22 | 日本曹達株式会社 | Photocatalyst layer forming composition |
| JP5189851B2 (en) * | 2008-02-14 | 2013-04-24 | 東京応化工業株式会社 | Composition for forming inorganic coating |
| JP2010099647A (en) * | 2008-03-28 | 2010-05-06 | Toto Ltd | Photocatalyst-coated body and photocatalytic coating liquid for the same |
| JP5313051B2 (en) * | 2008-06-09 | 2013-10-09 | 住友化学株式会社 | Zirconium oxalate sol |
| JP5849698B2 (en) * | 2011-12-29 | 2016-02-03 | Toto株式会社 | Composite and coating composition |
| JP2017042683A (en) * | 2014-03-03 | 2017-03-02 | 株式会社鯤コーポレーション | Photocatalyst coating liquid, and photocatalyst film using the same |
| JP6695417B2 (en) * | 2016-02-26 | 2020-05-20 | 日本曹達株式会社 | Photocatalyst structure and manufacturing method thereof |
| JP6370859B2 (en) * | 2016-10-31 | 2018-08-08 | 国立大学法人徳島大学 | Coating composition for plant growth regulation |
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