JP6969240B2 - Titanium oxide airgel particles, method for producing titanium oxide airgel particles, composition for forming a photocatalyst, photocatalyst, and structure. - Google Patents
Titanium oxide airgel particles, method for producing titanium oxide airgel particles, composition for forming a photocatalyst, photocatalyst, and structure. Download PDFInfo
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- JP6969240B2 JP6969240B2 JP2017173386A JP2017173386A JP6969240B2 JP 6969240 B2 JP6969240 B2 JP 6969240B2 JP 2017173386 A JP2017173386 A JP 2017173386A JP 2017173386 A JP2017173386 A JP 2017173386A JP 6969240 B2 JP6969240 B2 JP 6969240B2
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- titanium oxide
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- airgel particles
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 178
- 239000011941 photocatalyst Substances 0.000 title claims description 52
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- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 34
- 125000004429 atom Chemical group 0.000 claims description 32
- 239000011164 primary particle Substances 0.000 claims description 32
- 125000001931 aliphatic group Chemical group 0.000 claims description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 29
- 239000001569 carbon dioxide Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 28
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- 238000000862 absorption spectrum Methods 0.000 claims description 19
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- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
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Description
本発明は、酸化チタンエアロゲル粒子、酸化チタンエアロゲル粒子の製造方法、光触媒形成用組成物、光触媒、及び構造体に関する。 The present invention relates to titanium oxide airgel particles, a method for producing titanium oxide airgel particles, a composition for forming a photocatalyst, a photocatalyst, and a structure.
酸化チタン粒子は、光触媒として利用することが知られている。 Titanium oxide particles are known to be used as a photocatalyst.
例えば、特許文献１には、「凹凸表面を有する多孔質担体と、前記凹凸表面に担持される光触媒粒子と、を含む、光触媒複合体」が開示されている。特許文献１には、「光触媒粒子は、酸化チタン粒子および／または酸化タングステン粒子が好ましい」こと、「多孔質体は酸化ケイ素、活性炭、ゼオライトが好ましい」こと、「多孔質担体の空隙率は５０〜９５％が好ましい」ことも開示されている。 For example, Patent Document 1 discloses "a photocatalytic composite containing a porous carrier having an uneven surface and photocatalytic particles supported on the uneven surface". Patent Document 1 states that "the photocatalytic particles are preferably titanium oxide particles and / or tungsten oxide particles", "the porous body is preferably silicon oxide, activated carbon, and zeolite", and "the porosity of the porous carrier is 50". It is also disclosed that "~ 95% is preferable".
特許文献２には、「ポーラス材料（ゼオライト、シリカ、活性炭等）の上に光触媒溶射被膜(二酸化チタン（粒子）を形成した吸着剤」が開示されている。特許文献２には、「ポーラス材料と溶射被膜の間にはポーラス材料よりも大きな隙間があり、光触媒で分解できなかったものは吸着される」ことも開示されている。 Patent Document 2 discloses "an adsorbent in which a photocatalytic sprayed coating (titanium dioxide (particles) is formed" on a porous material (zeolite, silica, activated carbon, etc.)". Patent Document 2 discloses "porous material." There is a larger gap between the sprayed coating and the porous material than the porous material, and those that could not be decomposed by the photocatalyst are adsorbed. "
特許文献３には、「酸化チタンナノ分散液、吸着材、無機化合物分散液、シリカ化合物および金属微粒子を含む塗布用の吸着材‐光触媒ハイブリッド型脱臭材料であって、該無機化合物分散液は無機化合物が該吸着材の量に対して重量比で０．０２〜０．２含まれてなる吸着材‐光触媒ハイブリッド型脱臭材料」が開示されている。 Patent Document 3 states that "an adsorbent-photocatalyst hybrid deodorizing material for coating containing a titanium oxide nanodisperse, an adsorbent, an inorganic compound dispersion, a silica compound and metal fine particles, wherein the inorganic compound dispersion is an inorganic compound. Is disclosed as an adsorbent-photocatalyst hybrid deodorizing material containing 0.02 to 0.2 by weight with respect to the amount of the adsorbent.
特許文献４には、「アンモニア分解能を有する金属粒子と、金属粒子の粒径よりも小さな径の細孔を有しかつ金属粒子と接触する多孔質材料と、を有するアンモニア分解触媒」が開示されている。特許文献４には、「金属粒子は、遷移金属又は貴金属の粒子であり、多孔質材料は、ＺＳＭ５、シリカライト、チタン含有ゼオライトから選ばれた少なくとも１つである」こと、「担体は、モルデナイト、ＺＳＭ５、フェリエライト、ベータ型ゼオライト、Ｙ型ゼオライト、から選ばれた少なくとも１つである」も開示されている。 Patent Document 4 discloses "an ammonia decomposition catalyst having metal particles having ammonia resolution and a porous material having pores having a diameter smaller than the particle size of the metal particles and in contact with the metal particles". ing. Patent Document 4 states that "the metal particles are transition metal or noble metal particles, and the porous material is at least one selected from ZSM5, silicalite, and titanium-containing zeolite", and "the carrier is mordenite." , ZSM5, Ferrierite, Beta Zeolites, Y Zeolites, at least one selected from. "
特許文献５には、「金属酸化物を含有する担体に、ナノスケールの金属超微粒子を分散させた状態で固定してなる多孔質複合体」が開示されている。特許文献５には、「担体は、シリカ、アルミナ、チタニア、ジルコニア、又は、比表面積が２００ｍ２／ｇ以上あるエアロゲル若しくはキセロゲルである」ことが開示されている。 Patent Document 5 discloses "a porous complex in which nanoscale metal ultrafine particles are dispersed and fixed on a carrier containing a metal oxide". Patent Document 5 discloses that "the carrier is silica, alumina, titania, zirconia, or an airgel or xerogel having a specific surface area of 200 m 2 / g or more".
特許文献６には、可視光応答型光触媒酸化チタンと多孔質シリカとから形成された複合体であり、ＢＥＴ比表面積が２００〜１０００ｍ２／ｇ、細孔容積が０．１０〜１．０ｃｍ3／ｇ、細孔径が１〜１０ｎｍである、ことを特徴とする光触媒体」が開示されている。 Patent Document 6 describes a composite formed of visible light responsive photocatalyst titanium oxide and porous silica, having a BET specific surface area of 200 to 1000 m 2 / g and a pore volume of 0.10 to 1.0 cm 3 /. g, a photocatalyst characterized by having a pore diameter of 1 to 10 nm ”is disclosed.
特許文献７には、「多孔質基材と、多孔質基材の表面上に順次積層された酸化物粒子からなる第１のコート層、第２のコート層と、第２のコート層の上に設けられた触媒成分と、を備え、第１のコート層を構成する酸化物粒子の粒径は、前記第２のコート層を構成する酸化物粒子の粒径よりも大きい触媒体が開示されている。
また、特許文献７には、「多孔質基材はコージェライトであり、第１のコート層を構成する酸化物粒子の粒径は６００ｎｍ〜１０００ｎｍであり、第２のコート層を構成する酸化物粒子の粒径は、３０ｎｍ〜８０ｎｍであることが記載されている、
さらに、特許文献７には、第１および第２のコート層を構成する酸化物粒子は、ＣｅＯ２、ＺｒＯ２、Ａｌ２Ｏ３、ＴｉＯ２、ＳｉＯ２、ＭｇＯ、Ｙ２Ｏ３、Ｎｉ２Ｏ３およびこれらの組成物から選ばれる一種または二種以上の化合物のいずれかから構成されるものであることが記載されている。
Patent Document 7 states, "On the first coat layer, the second coat layer, and the second coat layer, which are composed of a porous base material and oxide particles sequentially laminated on the surface of the porous base material. Disclosed is a catalyst body comprising the catalyst component provided in the above, wherein the particle size of the oxide particles constituting the first coat layer is larger than the particle size of the oxide particles constituting the second coat layer. ing.
Further, in Patent Document 7, "the porous substrate is cordierite, the particle size of the oxide particles constituting the first coat layer is 600 nm to 1000 nm, and the oxide constituting the second coat layer is formed. It is stated that the particle size of the particles is 30 nm to 80 nm.
Further, in Patent Document 7, the oxide particles constituting the first and second coat layers are CeO 2 , ZrO 2 , Al 2 O 3 , TiO 2 , SiO 2 , MgO, Y 2 O 3 , and Ni 2. O 3 and it has been described that is intended to be composed of either one or two or more compounds selected from these compositions.
光触媒材料として普及している酸化チタン粒子は、紫外光を吸収することにより光触媒機能を発揮する。したがって、酸化チタン粒子は、紫外光を十分に確保できる晴れた日の昼間は光触媒機能を発揮できるものの、夜又は日陰では光触媒機能が低下する傾向がある。例えば、酸化チタン粒子を外壁材に用いた場合は、日向と日陰とで耐汚染性能に差が出ることがある。また、酸化チタン粒子を空気清浄機又は浄水器等に用いる際には、機器の内部に紫外線の光源となるブラックライト等を設置することが必要になる場合がある。上記事情に鑑み、可視光領域においても光触媒機能を発現する光触媒材料が求められている。 Titanium oxide particles, which are widely used as photocatalytic materials, exhibit a photocatalytic function by absorbing ultraviolet light. Therefore, the titanium oxide particles can exhibit the photocatalytic function in the daytime on a sunny day when sufficient ultraviolet light can be secured, but the photocatalytic function tends to decrease at night or in the shade. For example, when titanium oxide particles are used as the outer wall material, the stain resistance performance may differ between the sun and the shade. Further, when the titanium oxide particles are used in an air purifier, a water purifier, or the like, it may be necessary to install a black light or the like as a light source of ultraviolet rays inside the device. In view of the above circumstances, there is a demand for a photocatalytic material that exhibits a photocatalytic function even in the visible light region.
一方、光触媒機能を発現する比表面積を大きくする技術として、ゼオライト、シリカゲル等のミクロポーラス材料又はメソポーラス材料からなる多孔質材料の孔表面に光触媒粒子を付着させた光触媒材料が知られている。ただし、この光触媒材料においては、光触媒粒子が多孔質材料の孔入口を塞いだり、微細な孔内部には光が当たらなかったりして、光触媒機能が必ずしも向上しないことがある。 On the other hand, as a technique for increasing the specific surface area that exhibits a photocatalytic function, a photocatalytic material in which photocatalytic particles are attached to the pore surface of a porous material made of a microporous material such as zeolite or silica gel or a mesoporous material is known. However, in this photocatalytic material, the photocatalytic function may not necessarily be improved because the photocatalyst particles block the pore inlet of the porous material or the inside of the fine pores is not exposed to light.
そこで、本発明は、可視吸収スペクトルにおいて波長４５０ｎｍ未満にのみに吸収を持ち、ＢＥＴ比表面積が１２０未満である酸化チタン粒子に比べ、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子を提供することを課題とする。 Therefore, the present invention provides titanium oxide aerogel particles that have absorption only at a wavelength of less than 450 nm in the visible absorption spectrum and exhibit a higher photocatalytic function even in the visible light region than titanium oxide particles having a BET specific surface area of less than 120. The challenge is to provide.
前記課題を解決するための具体的手段には、下記の態様が含まれる。 Specific means for solving the above-mentioned problems include the following aspects.
＜１＞
金属原子及び炭化水素基を有する金属化合物が酸素原子を介して表面に結合しており、
ＢＥＴ比表面積が、１２０ｍ２／ｇ以上１０００ｍ２／ｇ以下であり、
可視吸収スペクトルにおいて波長４５０ｎｍ及び７５０ｎｍに吸収を持つ、
酸化チタンエアロゲル粒子。
< 1 >
Metal compound having a metallic atom and a hydrocarbon group is bound to the surface through an oxygen atom,
The BET specific surface area is 120 m 2 / g or more and 1000 m 2 / g or less.
Has absorption at wavelengths of 450 nm and 750 nm in the visible absorption spectrum.
Titanium oxide airgel particles.
＜２＞
可視吸収スペクトルにおいて波長４００ｎｍ以上８００ｎｍ以下の全範囲に吸収を持つ＜１＞に記載の酸化チタンエアロゲル粒子。
< 2 >
Titanium oxide airgel particles according to <1> having absorption in full range of wavelength equal to or more than 400 nm 800 nm in the visible absorption spectrum.
＜３＞
前記金属化合物が、金属原子と前記金属原子に直接結合した炭化水素基とを有する金属化合物である、＜１＞又は＜２＞に記載の酸化チタンエアロゲル粒子。
< 3 >
Before Symbol metal compound is a metal compound having a hydrocarbon group bonded directly to the metal atom and a metal atom, <1> or titanium oxide airgel particles according to <2>.
＜４＞
前記金属原子が、ケイ素原子である＜１＞〜＜３＞のいずれか１項に記載の酸化チタンエアロゲル粒子。
< 4 >
Before Symbol metal atom is a silicon atom <1> to titanium oxide airgel particles according to any one of <3>.
＜５＞
前記炭化水素基が、炭素数１以上２０以下の飽和若しくは不飽和の脂肪族炭化水素基又は炭素数６以上２０以下の芳香族炭化水素基である＜１＞〜＜４＞のいずれか１項に記載の酸化チタンエアロゲル粒子。
< 5 >
Before SL hydrocarbon group, either an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 6 to 20 carbon atoms, saturated or unsaturated 1 to 20 carbon atoms <1> to the <4> 1 The titanium oxide aerogel particles described in the section.
＜６＞
前記炭化水素基が、炭素数１以上２０以下の飽和脂肪族炭化水素基である＜５＞に記載の酸化チタンエアロゲル粒子。
< 6 >
Before SL hydrocarbon group, the titanium oxide airgel particles according to a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms <5>.
＜７＞
前記炭化水素基が、炭素数４以上１０以下の飽和脂肪族炭化水素基である＜６＞に記載の酸化チタンエアロゲル粒子。
< 7 >
Before SL hydrocarbon group, the titanium oxide airgel particles according to a saturated aliphatic hydrocarbon group having 4 to 10 carbon atoms <6>.
＜８＞
体積平均粒子径が０．１μｍ以上３μｍ以下、体積粒度分布が１．５以上１０以下である＜１＞〜＜７＞のいずれか１項に記載の酸化チタンエアロゲル粒子。
< 8 >
Body volume average particle diameter of 0.1μm or more 3μm or less, the volume particle size distribution of 1.5 to 10 <1> to titanium oxide airgel particles according to any one of <7>.
＜９＞
一次粒子が凝集した凝集粒子であり、平均一次粒子径が１ｎｍ以上１２０ｎｍ以下である＜１＞〜＜８＞のいずれか１項に記載の酸化チタンエアロゲル粒子。
< 9 >
The titanium oxide airgel particles according to any one of < 1 > to < 8 > , which are aggregated particles in which the primary particles are aggregated and have an average primary particle diameter of 1 nm or more and 120 nm or less.
＜１０＞
前記酸化チタンエアロゲル粒子のＢＥＴ比表面積が、１５０ｍ２／ｇ以上９００ｍ２／ｇ以下である＜１＞〜＜９＞のいずれか１項に記載の酸化チタンエアロゲル粒子。
< 10 >
Before SL BET specific surface area of the titanium oxide airgel particles is 150 meters 2 / g or more 900 meters 2 / g or less <1> to titanium oxide airgel particles according to any one of <9>.
＜１１＞
酸化チタンを含む多孔質粒子をゾルゲル法により造粒し、前記多孔質粒子及び溶媒を含有する分散液を調製する工程と、
超臨界二酸化炭素を用いて前記分散液から前記溶媒を除去する工程と、
前記溶媒を除去した後の前記多孔質粒子を、超臨界二酸化炭素中で、金属原子及び炭化水素基を有する金属化合物により表面処理する工程と、
記表面処理した後の前記多孔質粒子を加熱処理する工程と、
を含む、＜１＞〜＜１０＞のいずれか１項に記載の酸化チタンエアロゲル粒子の製造方法。
< 11 >
A step of the porous particles containing acid titanium granulated by the sol-gel method, to prepare a dispersion containing the porous particles and a solvent,
The step of removing the solvent from the dispersion liquid using supercritical carbon dioxide, and
A step of surface-treating the porous particles after removing the solvent with a metal compound having a metal atom and a hydrocarbon group in supercritical carbon dioxide.
The step of heat-treating the porous particles after the surface treatment and
The method for producing titanium oxide airgel particles according to any one of < 1 > to < 10 > , which comprises.
＜１２＞
＜１＞〜＜１０＞のいずれか１項に記載の酸化チタンエアロゲル粒子と、
分散媒及びバインダーからなる群から選ばれた少なくとも１種の化合物と、
を含む光触媒形成用組成物。
< 12 >
The titanium oxide airgel particles according to any one of <1 > to < 10 > and
At least one compound selected from the group consisting of a dispersion medium and a binder, and
A composition for forming a photocatalyst containing.
＜１３＞
＜１＞〜＜１０＞のいずれか１項に記載の酸化チタンエアロゲル粒子を含む、又は、からなる光触媒。
< 13 >
A photocatalyst containing or consisting of titanium oxide airgel particles according to any one of <1 > to < 10 >.
＜１４＞
＜１＞〜＜１０＞のいずれか１項に記載の酸化チタンエアロゲル粒子を有する構造体。
< 14 >
The structure having the titanium oxide airgel particles according to any one of <1 > to < 10 >.
＜１＞、又は＜２＞に係る発明によれば、可視吸収スペクトルにおいて波長４５０ｎｍ未満にのみに吸収を持ち、ＢＥＴ比表面積が１２０未満である酸化チタン粒子に比べ、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子が提供される。
＜３＞に係る発明によれば、金属化合物が、金属原子と金属原子に直接結合していない炭化水素基とを有する金属化合物である場合に比べ、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子が提供される。
＜４＞に係る発明によれば、金属化合物の金属原子がアルミニウム原子又はチタン原子である場合に比べて、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子が提供される。
＜５＞に係る発明によれば、炭化水素基が、炭素数２１以上の飽和若しくは不飽和の脂肪族炭化水素基又は２１以上の芳香族炭化水素基である場合に比べ、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子が提供される。
＜６＞に係る発明によれば、炭化水素基が、炭素数６以上２０以下の芳香族炭化水素基である場合に比べ、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子が提供される。
＜７＞に係る発明によれば、炭化水素基が、炭素数１１以上の飽和脂肪族炭化水素基である場合に比べ、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子が提供される。
＜８＞に係る発明によれば、酸化チタンエアロゲル粒子の体積平均粒子径が０．１μｍ未満、又は体積粒度分布が１．５未満である場合に比べ、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子が提供される。
＜９＞に係る発明によれば、酸化チタンエアロゲル粒子の平均一次粒子径が１２０ｎｍ超える場合に比べ、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子が提供される。
＜１０＞に係る発明によれば、酸化チタンエアロゲル粒子のＢＥＴ比表面積が１５０ｍ２／ｇ未満である場合に比べ、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子が提供される。
According to the invention according to < 1 > or < 2 > , a photocatalyst having absorption only at a wavelength of less than 450 nm in the visible absorption spectrum and having a higher photocatalyst in the visible light region than titanium oxide particles having a BET specific surface area of less than 120. Titanium oxide aerogel particles that exhibit function are provided.
According to the invention according to < 3 > , a higher photocatalytic function is exhibited even in the visible light region as compared with the case where the metal compound is a metal compound having a metal atom and a hydrocarbon group not directly bonded to the metal atom. Titanium oxide aerogel particles are provided.
According to the invention according to < 4 > , titanium oxide aerogel particles exhibiting a high photocatalytic function even in the visible light region as compared with the case where the metal atom of the metal compound is an aluminum atom or a titanium atom is provided.
According to the invention according to < 5 > , even in the visible light region, as compared with the case where the hydrocarbon group is a saturated or unsaturated aliphatic hydrocarbon group having 21 or more carbon atoms or an aromatic hydrocarbon group having 21 or more carbon atoms. Titanium oxide aerogel particles exhibiting high photocatalytic function are provided.
According to the invention according to < 6 > , titanium oxide airgel particles exhibiting a high photocatalytic function even in the visible light region as compared with the case where the hydrocarbon group is an aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms is provided. Will be done.
According to the invention according to < 7 > , titanium oxide airgel particles exhibiting a high photocatalytic function even in the visible light region as compared with the case where the hydrocarbon group is a saturated aliphatic hydrocarbon group having 11 or more carbon atoms are provided. NS.
According to the invention according to < 8 > , a higher photocatalytic function is exhibited even in the visible light region as compared with the case where the volume average particle size of the titanium oxide aerogel particles is less than 0.1 μm or the volume particle size distribution is less than 1.5. Titanium oxide aerogel particles are provided.
According to the invention according to < 9 > , titanium oxide airgel particles exhibiting a high photocatalytic function even in the visible light region as compared with the case where the average primary particle size of the titanium oxide airgel particles exceeds 120 nm are provided.
According to the invention according to < 10 > , titanium oxide airgel particles exhibiting a high photocatalytic function even in the visible light region are provided as compared with the case where the BET specific surface area of the titanium oxide airgel particles is less than 150 m 2 / g.
＜１１＞に係る発明によれば、分散液から溶媒を除去する工程を大気下で実施する場合、又は、金属原子及び炭化水素基を有する金属化合物により表面処理する工程を大気下で実施する場合に比べて、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子の製造方法が提供される。 According to the invention according to < 11 >, when the step of removing the solvent from the dispersion liquid is carried out in the atmosphere, or when the step of surface treatment with a metal compound having a metal atom and a hydrocarbon group is carried out in the atmosphere. A method for producing titanium oxide airgel particles, which exhibits a high photocatalytic function even in the visible light region, is provided.
＜１２＞、＜１３＞又は＜１４＞に係る発明によれば、可視吸収スペクトルにおいて波長４５０ｎｍ未満にのみに吸収を持ち、ＢＥＴ比表面積が１２０未満の酸化チタン粒子を適用した場合に比べて、可視光領域においても高い光触媒機能を発現する酸化チタンエアロゲル粒子を用いた光触媒形成用組成物、光触媒又は構造体が提供される。 According to the invention according to < 12 > , < 13 > or < 14 > , as compared with the case where titanium oxide particles having absorption only at a wavelength of less than 450 nm in the visible absorption spectrum and having a BET specific surface area of less than 120 are applied. Provided are a composition for forming a photocatalyst, a photocatalyst or a structure using titanium oxide aerogel particles that exhibit a high photocatalytic function even in the visible light region.
以下に、発明の実施形態を説明する。これらの説明及び実施例は実施形態を例示するものであり、発明の範囲を制限するものではない。 Hereinafter, embodiments of the invention will be described. These explanations and examples are illustrative of embodiments and do not limit the scope of the invention.
本明細書において、組成物中の各成分の量について言及する場合、組成物中に各成分に該当する物質が複数種存在する場合には、特に断らない限り、組成物中に存在する当該複数種の物質の合計量を意味する。
「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。
「ＸＰＳ」とは、X-ray Photoelectron Spectroscopy（Ｘ線光電子分光）の略である。
In the present specification, when the amount of each component in the composition is referred to, when a plurality of substances corresponding to each component are present in the composition, the plurality of substances present in the composition unless otherwise specified. It means the total amount of the substance of the seed.
The term "process" is included in this term not only in an independent process but also in the case where the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
"XPS" is an abbreviation for X-ray Photoelectron Spectroscopy.
＜酸化チタンエアロゲル粒子＞
本実施形態に係る酸化チタンエアロゲル粒子は、金属原子及び炭化水素基を有する金属化合物が酸素原子を介して表面に結合しており、ＢＥＴ比表面積が、１２０ｍ２／ｇ以上１０００ｍ２／ｇ以下であり、可視吸収スペクトルにおいて波長４５０ｎｍ及び７５０ｎｍに吸収を持つ。
<Titanium oxide airgel particles>
In the titanium oxide aerogel particles according to the present embodiment, a metal compound having a metal atom and a hydrocarbon group is bonded to the surface via an oxygen atom, and the BET specific surface area is 120 m 2 / g or more and 1000 m 2 / g or less. Yes, it has absorption at wavelengths of 450 nm and 750 nm in the visible absorption spectrum.
ここで、本実施形態に係る酸化チタンエアロゲル粒子の模式図を図１に示す。図１に示すように、本実施形態に係る酸化チタンエアロゲル粒子は、一次粒子が多孔構造を形成しつつ凝集したエアロゲル構造を有する。
なお、「エアロゲル」とは、一次粒子が多孔構造を形成しつつ凝集した構造を指す。そして、エアロゲル粒子の内部は、３次元網目状の微細構造となっており、数ｎｍの球状体が結合したクラスター構造を有する。
Here, a schematic diagram of titanium oxide airgel particles according to this embodiment is shown in FIG. As shown in FIG. 1, the titanium oxide airgel particles according to the present embodiment have an airgel structure in which the primary particles aggregate while forming a porous structure.
The term "airgel" refers to a structure in which primary particles are aggregated while forming a porous structure. The inside of the airgel particles has a three-dimensional network-like fine structure, and has a cluster structure in which spherical bodies of several nm are bonded.
本実施形態に係る酸化チタンエアロゲル粒子は、粒子中に多くの細孔、空隙を有することから、従来の非多孔質の酸化チタン粒子よりも粒径の割に高いＢＥＴ比表面積（１２０ｍ２／ｇ以上１０００ｍ２／ｇ以下のＢＥＴ比表面積）を有し、さらに有機金属化合物が酸素原子を介して表面に結合していることが相まって、可視吸収スペクトルにおいて波長４５０ｎｍ及び７５０ｎｍに吸収を持つ、即ち、酸化チタンエアロゲル粒子が可視光領域においても光触媒機能（つまり高い可視光応答性）を発現すると推測される。 Since the titanium oxide aerogel particles according to the present embodiment have many pores and voids in the particles, the BET specific surface area (120 m 2 / g) is higher than that of the conventional non-porous titanium oxide particles for the particle size. It has a BET specific surface area of 1000 m 2 / g or less), and further, coupled with the fact that the organic metal compound is bonded to the surface via oxygen atoms, it has absorption at wavelengths of 450 nm and 750 nm in the visible absorption spectrum, that is, It is presumed that the titanium oxide aerogel particles exhibit a photocatalytic function (that is, high visible light responsiveness) even in the visible light region.
具体的には、詳細な機序は不明であるが、炭化水素基が適度に酸化されている有機金属化合物が酸化チタンエアロゲル粒子表面および細孔内に存在することにより、酸化チタンエアロゲル粒子が波長４５０ｎｍ及び７５０ｎｍに光吸収性を示し、その結果、酸化チタンエアロゲル粒子が可視光領域においても光触媒機能を発現すると推測される。 Specifically, although the detailed mechanism is unknown, the titanium oxide aerogel particles have a wavelength due to the presence of an organic metal compound in which the hydrocarbon group is appropriately oxidized on the surface of the titanium oxide aerogel particles and in the pores. It is presumed that the titanium oxide aerogel particles exhibit a photocatalytic function even in the visible light region as a result of exhibiting light absorption at 450 nm and 750 nm.
また、酸化チタンエアロゲル粒子のＢＥＴ比表面積が１２０ｍ２／ｇ以上であると、量に対して比表面積が大きく、光触媒機能が高まる。酸化チタンエアロゲル粒子のＢＥＴ比表面積が１０００ｍ２／ｇ以下であると、粗大粒子（粒径が２０μｍを超える粒子）の割合が少なく、後述する光触媒形成用組成物、光触媒又は構造体において粒子分散性が向上し、高い光触媒機能が発現しやすい。このため、酸化チタンエアロゲル粒子のＢＥＴ比表面積を上記範囲にすると、可視光領域において高い光触媒機能を発現させやすくなる。
なお、上記の観点から、酸化チタンエアロゲル粒子のＢＥＴ比表面積は、１５０ｍ２／ｇ以上９００ｍ２／ｇ以下が好ましく、１８０ｍ２／ｇ以上８００ｍ２／ｇ以下が更に好ましい。
Further, when the BET specific surface area of the titanium oxide airgel particles is 120 m 2 / g or more, the specific surface area is large with respect to the amount, and the photocatalytic function is enhanced. When the BET specific surface area of the titanium oxide aerogel particles is 1000 m 2 / g or less, the proportion of coarse particles (particles having a particle size of more than 20 μm) is small, and the particle dispersibility in the photocatalyst-forming composition, photocatalyst or structure described later. Is improved, and a high photocatalytic function is likely to be exhibited. Therefore, when the BET specific surface area of the titanium oxide airgel particles is set within the above range, it becomes easy to exhibit a high photocatalytic function in the visible light region.
From the above viewpoint, the BET specific surface area of the titanium oxide airgel particles is preferably 150 m 2 / g or more and 900 m 2 / g or less, and more preferably 180 m 2 / g or more and 800 m 2 / g or less.
酸化チタンエアロゲル粒子のＢＥＴ比表面積は、窒素ガスを用いたガス吸着法により求める。詳細な測定方法は、後述の［実施例］に記載するとおりである。 The BET specific surface area of the titanium oxide airgel particles is determined by a gas adsorption method using nitrogen gas. The detailed measurement method is as described in [Example] described later.
さらに、本実施形態に係る酸化チタンエアロゲル粒子は、一次粒子が集合した多孔構造を持つ。そして、酸化チタンエアロゲル粒子の平均一次粒子径は１ｎｍ以上１２０ｎｍ以下がよい。平均一次粒子径が１ｎｍ以上であると、多孔構造を形成しつつ凝集した凝集粒子表面の細孔径が適度な大きさとなり、光分解対象物の吸着性が向上することにより、可視光領域における光触媒機能を発現させやすくなる。前記平均一次粒子径が１２０ｎｍ以下であると、一次粒子が多孔構造を形成しつつ凝集しエアロゲル構造を形成しやすくなることから、可視光領域において高い光触媒機能を発現させやすくなる。 Further, the titanium oxide airgel particles according to the present embodiment have a porous structure in which primary particles are aggregated. The average primary particle size of the titanium oxide airgel particles is preferably 1 nm or more and 120 nm or less. When the average primary particle diameter is 1 nm or more, the pore diameter on the surface of the aggregated particles aggregated while forming a porous structure becomes an appropriate size, and the adsorptivity of the photodecomposition target is improved, so that the photocatalyst in the visible light region It becomes easier to express the function. When the average primary particle diameter is 120 nm or less, the primary particles aggregate while forming a porous structure to easily form an airgel structure, so that a high photocatalytic function can be easily exhibited in the visible light region.
上記の観点から、酸化チタンエアロゲル粒子の平均一次粒子径は、５ｎｍ以上１００ｎｍが好ましく、１０ｎｍ以上９０ｎｍがさらに好ましい。 From the above viewpoint, the average primary particle size of the titanium oxide airgel particles is preferably 5 nm or more and 100 nm, and more preferably 10 nm or more and 90 nm.
本実施形態に係る酸化チタンエアロゲル粒子の体積平均粒子径は、０．１μｍ以上３μｍ以下がよい。体積平均粒子径が０．１μｍ以上であると、一次粒子が多孔構造を形成し高いＢＥＴ比表面積により光分解対象物の吸着性が向上し易い。それにより高い光触媒効果が発現され易くなる。体積平均粒子径が３μｍ以下であると、粗大粒子が少なく、後述する光触媒形成組成物、光触媒または構造体において酸化チタンエアロゲル粒子の分散性が向上し、光触媒機能が高まる。このため、酸化チタンエアロゲル粒子の体積平均粒子径を上記範囲にすると、可視光領域において高い光触媒機能を発現させ易くなる。 The volume average particle size of the titanium oxide airgel particles according to the present embodiment is preferably 0.1 μm or more and 3 μm or less. When the volume average particle diameter is 0.1 μm or more, the primary particles form a porous structure, and the high BET specific surface area tends to improve the adsorptivity of the photodegradable object. As a result, a high photocatalytic effect is likely to be exhibited. When the volume average particle diameter is 3 μm or less, the number of coarse particles is small, the dispersibility of the titanium oxide airgel particles is improved in the photocatalyst forming composition, the photocatalyst or the structure described later, and the photocatalyst function is enhanced. Therefore, when the volume average particle size of the titanium oxide airgel particles is set in the above range, it becomes easy to exhibit a high photocatalytic function in the visible light region.
上記の観点から、酸化チタンエアロゲル粒子の体積平均粒子径は、０．３μｍ以上２．８μｍ以下が好ましく、０．５μｍ以上２．５μｍ以下がより好ましい。 From the above viewpoint, the volume average particle size of the titanium oxide airgel particles is preferably 0.3 μm or more and 2.8 μm or less, and more preferably 0.5 μm or more and 2.5 μm or less.
本実施形態に係る酸化チタンエアロゲル粒子の体積粒度分布は、１．５以上１０以下がよい。体積粒度分布が１．５以上であると、一次粒子が多孔構造を形成し高いＢＥＴ比表面積により光分解対象物の吸着性が向上し易い。それにより高い光触媒効果が発現され易くなる。体積粒度分布が１０以下であると、粗大粒子が少なく、後述する光触媒形成組成物、光触媒または構造体において酸化チタンエアロゲル粒子の分散性が向上し、光触媒機能が高まる。このため、酸化チタンエアロゲル粒子の体積粒度分布を上記範囲にすると、可視光領域において高い光触媒機能を発現させ易くなる。 The volume particle size distribution of the titanium oxide airgel particles according to this embodiment is preferably 1.5 or more and 10 or less. When the volume particle size distribution is 1.5 or more, the primary particles form a porous structure, and the high BET specific surface area tends to improve the adsorptivity of the photodegradable object. As a result, a high photocatalytic effect is likely to be exhibited. When the volume particle size distribution is 10 or less, the number of coarse particles is small, the dispersibility of the titanium oxide airgel particles is improved in the photocatalyst forming composition, the photocatalyst or the structure described later, and the photocatalyst function is enhanced. Therefore, when the volume particle size distribution of the titanium oxide airgel particles is within the above range, it becomes easy to exhibit a high photocatalytic function in the visible light region.
上記の観点から、酸化チタンエアロゲル粒子の体積粒度分布は、２以上９以下が好ましく、３以上７以下がより好ましい。 From the above viewpoint, the volume particle size distribution of the titanium oxide airgel particles is preferably 2 or more and 9 or less, and more preferably 3 or more and 7 or less.
なお、本実施形態に係る酸化チタンエアロゲル粒子は、単に表面積が高いだけでなく、その多孔構造により分解対象物の捕捉性が高まるため、光触媒機能がより高まると推測される。 It is presumed that the titanium oxide airgel particles according to the present embodiment not only have a high surface area but also have a porous structure that enhances the capture property of the decomposition target, so that the photocatalytic function is further enhanced.
本実施形態に係る酸化チタンエアロゲル粒子の平均一次粒子径、体積平均粒子径、および体積粒度分布の測定方法は、後述の［実施例］に記載するとおりである。 The method for measuring the average primary particle size, the volume average particle size, and the volume particle size distribution of the titanium oxide aerogel particles according to the present embodiment is as described in [Example] described later.
本実施形態に係る酸化チタンエアロゲル粒子は、可視吸収スペクトルにおいて波長４５０ｎｍ及び７５０ｎｍに吸収を持つ。本実施形態に係る酸化チタンエアロゲル粒子は、可視光領域においても高い光触媒機能を発現する観点から、可視吸収スペクトルにおいて波長４５０ｎｍ、６００ｎｍ及び７５０ｎｍに吸収を持つことが好ましく、可視吸収スペクトルにおいて波長４５０ｎｍ以上７５０ｎｍ以下の全範囲に吸収を持つことがより好ましく、可視吸収スペクトルにおいて波長４００ｎｍ以上８００ｎｍ以下の全範囲に吸収を持つことが特に好ましい。 The titanium oxide airgel particles according to the present embodiment have absorption at wavelengths of 450 nm and 750 nm in the visible absorption spectrum. The titanium oxide aerogel particles according to the present embodiment preferably have absorption at wavelengths of 450 nm, 600 nm and 750 nm in the visible absorption spectrum, and have a wavelength of 450 nm or more in the visible absorption spectrum, from the viewpoint of exhibiting a high photocatalytic function even in the visible light region. It is more preferable to have absorption in the entire range of 750 nm or less, and it is particularly preferable to have absorption in the entire range of wavelengths of 400 nm or more and 800 nm or less in the visible absorption spectrum.
本実施形態に係る酸化チタンエアロゲル粒子は、可視光領域においても高い光触媒機能を発現する観点から、紫外可視吸収スペクトルにおいて、波長３５０ｎｍの吸光度を１としたとき、波長４５０ｎｍの吸光度が０．０２以上（より好ましくは０．１以上、更に好ましくは０．２以上）であることが好ましく、波長６００ｎｍの吸光度が０．０２以上（より好ましくは０．１以上、更に好ましくは０．２以上）であることが好ましく、波長７５０ｎｍの吸光度が０．０２以上（より好ましくは０．１以上、更に好ましくは０．２以上）であることが好ましい。 The titanium oxide aerogel particles according to the present embodiment have an absorbance at a wavelength of 450 nm of 0.02 or more when the absorbance at a wavelength of 350 nm is 1 in the ultraviolet-visible absorption spectrum from the viewpoint of exhibiting a high photocatalytic function even in the visible light region. (More preferably 0.1 or more, still more preferably 0.2 or more), and the absorbance at a wavelength of 600 nm is 0.02 or more (more preferably 0.1 or more, still more preferably 0.2 or more). It is preferable that the absorbance at a wavelength of 750 nm is 0.02 or more (more preferably 0.1 or more, still more preferably 0.2 or more).
酸化チタンエアロゲル粒子の紫外可視吸収スペクトルは、波長２００ｎｍ乃至９００ｎｍの範囲の拡散反射スペクトルを測定し、拡散反射スペクトルからKubelka-Munk変換により理論的に各波長における吸光度を求めて得る。詳細な測定方法は、後述の［実施例］に記載するとおりである。 The ultraviolet-visible absorption spectrum of the titanium oxide aerogel particles is obtained by measuring the diffuse reflection spectrum in the wavelength range of 200 nm to 900 nm and theoretically obtaining the absorbance at each wavelength from the diffuse reflection spectrum by Kubelka-Munk conversion. The detailed measurement method is as described in [Example] described later.
本実施形態に係る酸化チタンエアロゲル粒子は、未処理の酸化チタンエアロゲル粒子を、金属原子及び炭化水素基を有する金属化合物により表面処理し、そして、加熱処理により前記炭化水素基の一部を酸化してなる酸化チタンエアロゲル粒子であることが好ましい。本明細書において、有機金属化合物により表面処理されていない酸化チタンエアロゲル粒子を「未処理の酸化チタンエアロゲル粒子」という。また、金属原子及び炭化水素基を有する金属化合物を「有機金属化合物」という。 In the titanium oxide aerogel particles according to the present embodiment, untreated titanium oxide aerogel particles are surface-treated with a metal compound having a metal atom and a hydrocarbon group, and a part of the hydrocarbon group is oxidized by heat treatment. It is preferably titanium oxide aerogel particles. In the present specification, titanium oxide airgel particles that have not been surface-treated with an organometallic compound are referred to as "untreated titanium oxide airgel particles". Further, a metal compound having a metal atom and a hydrocarbon group is referred to as an "organic metal compound".
［未処理の酸化チタンエアロゲル粒子］
未処理の酸化チタンエアロゲル粒子は、有機金属化合物により表面処理されていない酸化チタンエアロゲル粒子であり、他の表面処理を除外するものではない。本実施形態において未処理の酸化チタンエアロゲル粒子は、有機金属化合物による表面処理も、他の表面処理も、されていない酸化チタンエアロゲル粒子であることが好ましい。
[Untreated titanium oxide airgel particles]
The untreated titanium oxide airgel particles are titanium oxide airgel particles that have not been surface-treated with an organometallic compound, and do not exclude other surface treatments. In the present embodiment, the untreated titanium oxide airgel particles are preferably titanium oxide airgel particles that have not been surface-treated with an organometallic compound or other surface treatments.
未処理の酸化チタンエアロゲル粒子のＢＥＴ比表面積は、高い光触媒機能を発現する観点から、１２０ｍ２／ｇ以上１０００ｍ２／ｇ以下が好ましく、１５０ｍ２／ｇ以上９００ｍ２／ｇ以下がより好ましく、１８０ｍ２／ｇ以上８００ｍ２／ｇ以下が更に好ましい。 The BET specific surface area of the untreated titanium oxide airgel particles is preferably 120 m 2 / g or more and 1000 m 2 / g or less, more preferably 150 m 2 / g or more and 900 m 2 / g or less, and 180 m from the viewpoint of exhibiting a high photocatalytic function. 2 / g or more 800 m 2 / g or less is more preferable.
未処理の酸化チタンエアロゲル粒子の平均一次粒子径は、高い光触媒機能を発現する観点から、１ｎｍ以上１２０ｎｍ以下が好ましく、５ｎｍ以上１００ｎｍ以下がより好ましく、１０ｎｍ以上９０ｎｍ以下が更に好ましい。 The average primary particle size of the untreated titanium oxide airgel particles is preferably 1 nm or more and 120 nm or less, more preferably 5 nm or more and 100 nm or less, and further preferably 10 nm or more and 90 nm or less from the viewpoint of exhibiting a high photocatalytic function.
未処理の酸化チタンエアロゲル粒子の体積平均粒子径は、０．１μｍ以上３μｍ以下が好ましく、０．３μｍ以上２．８μｍ以下がより好ましく、０．５μｍ以上２.５μｍ以下がさらに好ましい。 The volume average particle diameter of the untreated titanium oxide airgel particles is preferably 0.1 μm or more and 3 μm or less, more preferably 0.3 μm or more and 2.8 μm or less, and further preferably 0.5 μm or more and 2.5 μm or less.
未処理の酸化チタンエアロゲル粒子の製造方法は、特に制限されないが、ＢＥＴ比表面積の範囲を前記範囲に制御する観点から、チタンアルコキシドを材料に用いたゾルゲル法が好ましい。ゾルゲル法によって製造された酸化チタンエアロゲル粒子は、分散液中において、一次粒子が凝集して多孔構造を有する多孔質粒子（酸化チタンを含む多孔質粒子）を形成しており、前記範囲のＢＥＴ比表面積を実現できる。 The method for producing untreated titanium oxide airgel particles is not particularly limited, but a sol-gel method using titanium alkoxide as a material is preferable from the viewpoint of controlling the range of the BET specific surface area to the above range. The titanium oxide airgel particles produced by the sol-gel method have primary particles aggregated to form porous particles having a porous structure (porous particles containing titanium oxide) in the dispersion liquid, and have a BET ratio in the above range. A surface area can be realized.
未処理の酸化チタンエアロゲル粒子は、チタンアルコキシドの加水分解縮合物からなることが好ましい。ただし、チタンアルコキシドのアルコキシ基の一部が未反応のまま粒子に残留していてもよい。 The untreated titanium oxide airgel particles are preferably made of a hydrolyzed condensate of titanium alkoxide. However, some of the alkoxy groups of the titanium alkoxide may remain unreacted in the particles.
未処理の酸化チタンエアロゲル粒子は、ケイ素やアルミニウム等のチタン以外の金属元素を少量含んでもよい。なお、ケイ素元素を含む場合、ケイ素とチタンとの元素比Ｓｉ／Ｔｉが０．０５以下までは、酸化チタンエアロゲル粒子の可視光領域における高い光触媒機能を発現する効果への影響は少ない。 The untreated titanium oxide airgel particles may contain a small amount of metal elements other than titanium such as silicon and aluminum. When the element of silicon is contained, the effect on the effect of exhibiting a high photocatalytic function in the visible light region of the titanium oxide airgel particles is small until the element ratio Si / Ti of silicon and titanium is 0.05 or less.
酸化チタンエアロゲル粒子の結晶構造は、ブルッカイト型、アナターゼ型、ルチル型のいずれでもよく、これらの単結晶構造を有してもよく、これらが共存する混晶構造を有してもよい。酸化チタンエアロゲル粒子の結晶構造は、加熱処理温度の高低を調整することにより制御できる。 The crystal structure of the titanium oxide aerogel particles may be any of brookite type, anatase type and rutile type, may have a single crystal structure thereof, or may have a mixed crystal structure in which they coexist. The crystal structure of the titanium oxide airgel particles can be controlled by adjusting the temperature of the heat treatment.
［有機金属化合物］
本実施形態に係る酸化チタンエアロゲル粒子の表面には、有機金属化合物が酸素原子を介して結合している。有機金属化合物は、可視光応答性をより発現しやすい観点から、金属原子、炭素原子、水素原子及び酸素原子のみからなる金属化合物であることが好ましい。
[Organometallic compounds]
An organometallic compound is bonded to the surface of the titanium oxide airgel particles according to the present embodiment via oxygen atoms. The organic metal compound is preferably a metal compound consisting only of a metal atom, a carbon atom, a hydrogen atom and an oxygen atom from the viewpoint of more easily exhibiting visible light responsiveness.
有機金属化合物は、可視光応答性をより発現しやすい観点から、該有機金属化合物中の金属原子Ｍに直接結合した酸素原子Ｏを介して酸化チタンエアロゲル粒子の表面に結合していること、即ち、Ｍ−Ｏ−Ｔｉなる共有結合によって酸化チタンエアロゲル粒子の表面に結合していることが好ましい。 The organometallic compound is bonded to the surface of the titanium oxide aerogel particles via the oxygen atom O directly bonded to the metal atom M in the organometallic compound from the viewpoint of more easily exhibiting visible light responsiveness, that is, , M—O—Ti is preferably bonded to the surface of titanium oxide aerogel particles by a covalent bond.
有機金属化合物としては、可視光応答性をより発現しやすい観点から、金属原子Ｍと金属原子Ｍに直接結合した炭化水素基とを有する有機金属化合物が好ましい。該有機金属化合物は、該有機金属化合物中の金属原子Ｍに直接結合した酸素原子Ｏを介して酸化チタンエアロゲル粒子の表面に結合していることが好ましい。即ち、酸化チタンエアロゲル粒子の表面には、可視光応答性をより発現しやすい観点から、炭化水素基と、金属原子Ｍと、酸素原子Ｏと、チタン原子Ｔｉとが共有結合で順に連なった構造（炭化水素基−Ｍ−Ｏ−Ｔｉ）が存在することが好ましい。 As the organic metal compound, an organic metal compound having a metal atom M and a hydrocarbon group directly bonded to the metal atom M is preferable from the viewpoint of more easily exhibiting visible light responsiveness. The organometallic compound is preferably bonded to the surface of the titanium oxide airgel particles via the oxygen atom O directly bonded to the metal atom M in the organometallic compound. That is, on the surface of the titanium oxide aerogel particles, from the viewpoint of more easily exhibiting visible light responsiveness, a hydrocarbon group, a metal atom M, an oxygen atom O, and a titanium atom Ti are sequentially linked by a covalent bond. It is preferable that (hydrocarbon group-MO-Ti) is present.
有機金属化合物が複数個の炭化水素基を有する場合、少なくとも１個の炭化水素基が、該有機金属化合物中の金属原子に直接結合していることが好ましい。 When the organometallic compound has a plurality of hydrocarbon groups, it is preferable that at least one hydrocarbon group is directly bonded to a metal atom in the organometallic compound.
有機金属化合物における原子間の化学結合状態は、ＸＰＳの高分解能分析（ナロースキャン分析）を行うことにより知ることができる。 The chemical bond state between atoms in an organometallic compound can be known by performing high-resolution analysis (narrow scan analysis) of XPS.
有機金属化合物の金属原子としては、ケイ素、アルミニウム又はチタンが好ましく、ケイ素又はアルミニウムがより好ましく、ケイ素が特に好ましい。 As the metal atom of the organometallic compound, silicon, aluminum or titanium is preferable, silicon or aluminum is more preferable, and silicon is particularly preferable.
有機金属化合物が有する炭化水素基としては、炭素数１以上４０以下（好ましくは炭素数１以上２０以下、より好ましくは炭素数１以上１８以下、更に好ましくは炭素数４以上１２以下、更に好ましくは炭素数４以上１０以下）の飽和若しくは不飽和の脂肪族炭化水素基、炭素数６以上２７以下（好ましくは炭素数６以上２０以下、より好ましくは炭素数６以上１８以下、更に好ましくは炭素数６以上１２以下、更に好ましくは炭素数６以上１０以下）の芳香族炭化水素基が挙げられる。 The hydrocarbon group contained in the organic metal compound has 1 or more and 40 or less carbon atoms (preferably 1 or more and 20 or less carbon atoms, more preferably 1 or more and 18 or less carbon atoms, still more preferably 4 or more and 12 or less carbon atoms, still more preferably. Saturated or unsaturated aliphatic hydrocarbon groups having 4 or more and 10 or less carbon atoms, 6 or more and 27 or less carbon atoms (preferably 6 or more and 20 or less carbon atoms, more preferably 6 or more and 18 or less carbon atoms, still more preferably carbon atoms. Examples thereof include aromatic hydrocarbon groups having 6 or more and 12 or less, more preferably 6 or more and 10 or less carbon atoms).
有機金属化合物が有する炭化水素基は、高い光触媒機能の発現及び分散性の向上の観点から、脂肪族炭化水素基であることが好ましく、飽和脂肪族炭化水素基であることがより好ましく、アルキル基であることが特に好ましい。脂肪族炭化水素基は、直鎖状、分岐鎖状及び環状のいずれでもよいが、分散性の観点から、直鎖状又は分岐鎖状が好ましい。脂肪族炭化水素基の炭素数は、１以上２０以下が好ましく、１以上１８以下がより好ましく、４以上１２以下が更に好ましく、４以上１０以下が更に好ましい。 The hydrocarbon group contained in the organic metal compound is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group, and more preferably an alkyl group, from the viewpoint of exhibiting a high photocatalyst function and improving dispersibility. Is particularly preferable. The aliphatic hydrocarbon group may be linear, branched or cyclic, but is preferably linear or branched from the viewpoint of dispersibility. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 or more and 20 or less, more preferably 1 or more and 18 or less, further preferably 4 or more and 12 or less, and further preferably 4 or more and 10 or less.
有機金属化合物としては、炭化水素基を有するシラン化合物が特に好ましい。炭化水素基を有するシラン化合物としては、例えば、クロロシラン化合物、アルコキシシラン化合物、シラザン化合物（ヘキサメチルジシラザン等）などが挙げられる。 As the organometallic compound, a silane compound having a hydrocarbon group is particularly preferable. Examples of the silane compound having a hydrocarbon group include a chlorosilane compound, an alkoxysilane compound, and a silazane compound (hexamethyldisilazane and the like).
酸化チタンエアロゲル粒子の表面処理に用いる、炭化水素基を有するシラン化合物としては、高い光触媒機能の発揮及び分散性の向上の観点から、式（１）：Ｒ１ ｎＳｉＲ２ ｍで表される化合物が好ましい。 The silane compound having a hydrocarbon group used for the surface treatment of titanium oxide airgel particles is a compound represented by the formula (1): R 1 n SiR 2 m from the viewpoint of exhibiting a high photocatalytic function and improving dispersibility. Is preferable.
式（１）：Ｒ１ ｎＳｉＲ２ ｍにおいて、Ｒ１は炭素数１以上２０以下の飽和若しくは不飽和の脂肪族炭化水素基又は炭素数６以上２０以下の芳香族炭化水素基を表し、Ｒ２はハロゲン原子又はアルコキシ基を表し、ｎは１以上３以下の整数を表し、ｍは１以上３以下の整数を表し、但しｎ＋ｍ＝４である。ｎが２又は３の整数である場合、複数のＲ１は同じ基でもよいし、異なる基でもよい。ｍが２又は３の整数である場合、複数のＲ２は同じ基でもよいし、異なる基でもよい。 Formula (1): In R 1 n SiR 2 m , R 1 represents a saturated or unsaturated aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms or an aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms. 2 represents a halogen atom or an alkoxy group, n represents an integer of 1 or more and 3 or less, m represents an integer of 1 or more and 3 or less, where n + m = 4. If n is an integer of 2 or 3, a plurality of R 1 are may be the same group or a different group. when m is an integer of 2 or 3, plural of R 2 may be the same group or a different group.
Ｒ１で表される脂肪族炭化水素基は、直鎖状、分岐鎖状及び環状のいずれでもよいが、分散性の観点から、直鎖状又は分岐鎖状が好ましい。脂肪族炭化水素基の炭素数は、高い光触媒機能の発現及び分散性の向上の観点から、炭素数１以上２０以下が好ましく、炭素数１以上１８以下がより好ましく、炭素数４以上１２以下が更に好ましく、炭素数４以上１０以下が更に好ましい。脂肪族炭化水素基は、飽和及び不飽和のいずれでもよいが、高い光触媒機能の発現及び分散性の向上の観点から、飽和脂肪族炭化水素基が好ましく、アルキル基がより好ましい。 The aliphatic hydrocarbon group represented by R 1 may be linear, branched or cyclic, but is preferably linear or branched from the viewpoint of dispersibility. The carbon number of the aliphatic hydrocarbon group is preferably 1 or more and 20 or less, more preferably 1 or more and 18 or less, and 4 or more and 12 or less carbons, from the viewpoint of exhibiting a high photocatalyst function and improving dispersibility. More preferably, the number of carbon atoms is 4 or more and 10 or less. The aliphatic hydrocarbon group may be saturated or unsaturated, but a saturated aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable, from the viewpoint of exhibiting a high photocatalyst function and improving dispersibility.
飽和脂肪族炭化水素基としては、直鎖状アルキル基（メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、ヘキサデシル基、イコシル基等）、分岐鎖状アルキル基（イソプロピル基、イソブチル基、イソペンチル基、ネオペンチル基、２−エチルヘキシル基、ターシャリーブチル基、ターシャリーペンチル基、イソペンタデシル基等）、環状アルキル基（シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、トリシクロデシル基、ノルボルニル基、アダマンチル基等）などが挙げられる。 Saturated aliphatic hydrocarbon groups include linear alkyl groups (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and hexadecyl group. , Icosyl group, etc.), branched chain alkyl group (isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, tertiary butyl group, tertiary pentyl group, isopentadecyl group, etc.), cyclic alkyl group ( Cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecyl group, norbornyl group, adamantyl group, etc.) and the like can be mentioned.
不飽和脂肪族炭化水素基としては、アルケニル基（ビニル基（エテニル基）、１−プロペニル基、２−プロペニル基、２−ブテニル基、１−ブテニル基、１−ヘキセニル基、２−ドデセニル基、ペンテニル基等）、アルキニル基（エチニル基、１−プロピニル基、２−プロピニル基、１−ブチニル基、３−ヘキシニル基、２−ドデシニル基等）などが挙げられる。 Examples of the unsaturated aliphatic hydrocarbon group include an alkenyl group (vinyl group (ethenyl group), 1-propenyl group, 2-propenyl group, 2-butenyl group, 1-butenyl group, 1-hexenyl group, 2-dodecenyl group, (Pentenyl group, etc.), alkynyl group (ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 3-hexynyl group, 2-dodecynyl group, etc.) and the like.
脂肪族炭化水素基は、置換された脂肪族炭化水素基も含む。脂肪族炭化水素基に置換し得る置換基としては、ハロゲン原子、エポキシ基、グリシジル基、グリシドキシ基、メルカプト基、メタクリロイル基、アクリロイル基等が挙げられる。 Aliphatic hydrocarbon groups also include substituted aliphatic hydrocarbon groups. Examples of the substituent that can be substituted with the aliphatic hydrocarbon group include a halogen atom, an epoxy group, a glycidyl group, a glycidoxy group, a mercapto group, a methacryloyl group, an acryloyl group and the like.
Ｒ１で表される芳香族炭化水素基は、炭素数６以上２０以下が好ましく、より好ましくは炭素数６以上１８以下、更に好ましくは炭素数６以上１２以下、特に好ましくは炭素数６以上１０以下である。 Aromatic hydrocarbon group represented by R 1 preferably has 6 to 20 carbon atoms, more preferably 6 to 18 carbon atoms, more preferably having 6 to 12 carbon atoms, particularly preferably 6 or more carbon atoms 10 It is as follows.
芳香族炭化水素基としては、フェニレン基、ビフェニレン基、ターフェニレン基、ナフタレン基、アントラセン基等が挙げられる。 Examples of the aromatic hydrocarbon group include a phenylene group, a biphenylene group, a terphenylene group, a naphthalene group, an anthracene group and the like.
芳香族炭化水素基は、置換された芳香族炭化水素基も含む。芳香族炭化水素基に置換し得る置換基としては、ハロゲン原子、エポキシ基、グリシジル基、グリシドキシ基、メルカプト基、メタクリロイル基、アクリロイル基等が挙げられる。 Aromatic hydrocarbon groups also include substituted aromatic hydrocarbon groups. Examples of the substituent that can be substituted with the aromatic hydrocarbon group include a halogen atom, an epoxy group, a glycidyl group, a glycidoxy group, a mercapto group, a methacryloyl group, an acryloyl group and the like.
Ｒ２で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。ハロゲン原子としては、塩素原子、臭素原子、又はヨウ素原子が好ましい。 Examples of the halogen atom represented by R 2 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. As the halogen atom, a chlorine atom, a bromine atom, or an iodine atom is preferable.
Ｒ２で表されるアルコキシ基としては、炭素数１以上１０以下（好ましくは１以上８以下、より好ましくは３以上８以下）のアルコキシ基が挙げられる。アルコキシ基としては、メトキシ基、エトキシ基、イソプロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｎ−ヘキシロキシ基、２−エチルヘキシロキシ基、３，５，５−トリメチルヘキシルオキシ基等が挙げられる。アルコキシ基は、置換されたアルコキシ基も含む。アルコキシ基に置換し得る置換基としては、ハロゲン原子、水酸基、アミノ基、アルコキシ基、アミド基、カルボニル基等が挙げられる。 The alkoxy group represented by R 2, the number 1 to 10 carbon atoms (preferably 1 to 8, more preferably 3 to 8) and an alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-butoxy group, an n-hexyloxy group, a 2-ethylhexyloxy group, a 3,5,5-trimethylhexyloxy group and the like. Be done. Alkoxy groups also include substituted alkoxy groups. Examples of the substituent that can be substituted with the alkoxy group include a halogen atom, a hydroxyl group, an amino group, an alkoxy group, an amide group, a carbonyl group and the like.
式（１）：Ｒ１ ｎＳｉＲ２ ｍで表される化合物は、高い光触媒機能の発現及び分散性の向上の観点から、Ｒ１が飽和脂肪族炭化水素基である化合物が好ましい。特に、式（１）：Ｒ１ ｎＳｉＲ２ ｍで表される化合物は、Ｒ１が炭素数１以上２０以下の飽和脂肪族炭化水素基であり、Ｒ２がハロゲン原子又はアルコキシ基であり、ｎが１以上３以下の整数であり、ｍが１以上３以下の整数であり、但しｎ＋ｍ＝４であることが好ましい。 The compound represented by the formula (1): R 1 n SiR 2 m is preferably a compound in which R 1 is a saturated aliphatic hydrocarbon group from the viewpoint of expressing a high photocatalytic function and improving dispersibility. In particular, in the compound represented by the formula (1): R 1 n SiR 2 m , R 1 is a saturated aliphatic hydrocarbon group having 1 or more carbon atoms and 20 or less carbon atoms, and R 2 is a halogen atom or an alkoxy group. It is preferable that n is an integer of 1 or more and 3 or less, m is an integer of 1 or more and 3 or less, and n + m = 4.
式（１）：Ｒ１ ｎＳｉＲ２ ｍで表される化合物として、例えば、ビニルトリメトキシシラン、メチルトリメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、ブチルトリメトキシシラン、ヘキシルトリメトキシシラン、ｎ−オクチルトリメトキシシラン、デシルトリメトキシシラン、ドデシルトリメトキシシラン、ビニルトリエトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン、ブチルトリエトキシシラン、ヘキシルトリエトキシシラン、デシルトリエトキシシラン、ドデシルトリエトキシシラン、フェニルトリメトキシシラン、ｏ−メチルフェニルトリメトキシシラン、ｐ−メチルフェニルトリメトキシシラン、フェニルトリエトキシシラン、ベンジルトリエトキシシラン、デシルトリクロロシラン、フェニルトリクロロシラン（以上、ｎ＝１、ｍ＝３）；
ジメチルジメトキシシラン、ジメチルジエトキシシラン、メチルビニルジメトキシシラン、メチルビニルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、ジメチルジクロロシラン、ジクロロジフェニルシラン（以上、ｎ＝２、ｍ＝２）；
トリメチルメトキシシラン、トリメチルエトキシシラン、トリメチルクロロシラン、デシルジメチルクロロシラン、トリフェニルクロロシラン（以上、ｎ＝３、ｍ＝１）；
３−グリシドキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−（２−アミノエチル）アミノプロピルメチルジメトキシシラン、γ−グリシジルオキシプロピルメチルジメトキシシラン（以上、Ｒ１が、置換された脂肪族炭化水素基又は置換された芳香族炭化水素基である化合物）；
などのシラン化合物が挙げられる。シラン化合物は、１種単独で用いてもよいし、２種以上を併用してもよい。
Formula (1): Examples of the compound represented by R 1 n SiR 2 m include vinyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, and hexyltrimethoxysilane. n-octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, vinyltriethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, hexyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane Silane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, decyltrichlorosilane, phenyltrichlorosilane (above, n = 1, m = 3) );
Didimethyldimethoxysilane, dimethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldichlorosilane, dichlorodiphenylsilane (above, n = 2, m = 2);
Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, decyldimethylchlorosilane, triphenylchlorosilane (above, n = 3, m = 1);
3-Glysidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane , Γ- (2-Aminoethyl) Aminopropyltrimethoxysilane, γ- (2-Aminoethyl) Aminopropylmethyldimethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane (above, R 1 substituted aliphatic hydrocarbons) Compounds that are hydrogen groups or substituted aromatic hydrocarbon groups);
Examples thereof include silane compounds such as. The silane compound may be used alone or in combination of two or more.
式（１）で表されるシラン化合物における炭化水素基は、高い光触媒機能の発現及び分散性の向上の観点から、脂肪族炭化水素基であることが好ましく、飽和脂肪族炭化水素基であることがより好ましく、アルキル基であることが特に好ましい。上記シラン化合物における炭化水素基は、高い光触媒機能の発現及び分散性の向上の観点から、炭素数１以上２０以下の飽和脂肪族炭化水素基が好ましく、炭素数１以上１８以下の飽和脂肪族炭化水素基がより好ましく、炭素数４以上１２以下の飽和脂肪族炭化水素基が更に好ましく、炭素数４以上１０以下の飽和脂肪族炭化水素基が特に好ましい。 The hydrocarbon group in the silane compound represented by the formula (1) is preferably an aliphatic hydrocarbon group, preferably a saturated aliphatic hydrocarbon group, from the viewpoint of exhibiting a high photocatalyst function and improving dispersibility. Is more preferable, and an alkyl group is particularly preferable. The hydrocarbon group in the silane compound is preferably a saturated aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms, and a saturated aliphatic hydrocarbon having 1 or more and 18 or less carbon atoms, from the viewpoint of exhibiting a high photocatalyst function and improving dispersibility. A hydrogen group is more preferable, a saturated aliphatic hydrocarbon group having 4 or more and 12 or less carbon atoms is further preferable, and a saturated aliphatic hydrocarbon group having 4 or more and 10 or less carbon atoms is particularly preferable.
有機金属化合物の金属原子がアルミニウムである化合物としては、例えば、ジ−ｉ−プロポキシアルミニウム・エチルアセトアセテート等のアルミニウムキレート；アセトアルコキシアルミニウムジイソプロピレート等のアルミネート系カップリング剤；などが挙げられる。 Examples of the compound in which the metal atom of the organic metal compound is aluminum include aluminum chelates such as di-i-propoxyaluminum and ethylacetoacetate; and aluminate-based coupling agents such as acetoalkoxyaluminum diisopropyrate; ..
有機金属化合物の金属原子がチタンである化合物としては、例えば、イソプロピルトリイソステアロイルチタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート等のチタネート系カップリング剤；ジ−ｉ−プロポキシビス（エチルアセトアセテート）チタニウム、ジ−ｉ−プロポキシビス（アセチルアセトナート）チタニウム、ジ−ｉ−プロポキシビス（トリエタノールアミナート）チタニウム、ジ−ｉ−プロポキシチタンジアセテート、ジ−ｉ−プロポキシチタンジプロピオネート等のチタニウムキレート；などが挙げられる。 Examples of the compound in which the metal atom of the organic metal compound is titanium include titanium-based coupling agents such as isopropyltriisostearoyl titanate, tetraoctylbis (ditridecylphosphite) titanate, and bis (dioctylpyrophosphate) oxyacetate titanate; Di-i-propoxybis (ethylacetate acetate) titanium, di-i-propoxybis (acetylacetonate) titanium, di-i-propoxybis (triethanolaminate) titanium, di-i-propoxytitanium diacetate, di -I-Titanium chelate such as propoxytitanium dipropionate; and the like.
有機金属化合物は、１種単独で用いてもよいし、２種以上を併用してもよい。 The organometallic compound may be used alone or in combination of two or more.
有機金属化合物が表面に結合した酸化チタンエアロゲル粒子は、可視光領域においても高い光触媒機能を発現することに加えて、下記の観点からも有利である。 Titanium oxide airgel particles having an organometallic compound bonded to the surface are advantageous from the following viewpoints in addition to exhibiting a high photocatalytic function even in the visible light region.
一般的に、酸化チタンエアロゲル粒子は、樹脂中又は溶媒中での分散性がよくなく、それ故、塗膜の均一性が低く、光触媒機能が発揮されにくい傾向がある。
これに対して、有機金属化合物が表面に結合した酸化チタンエアロゲル粒子は、表面に有機金属化合物に由来する炭化水素基を有する故に、樹脂中又は溶媒中での分散性がよい。したがって、均一に近い塗膜が形成でき、効率よく酸化チタンエアロゲル粒子に光が当たり、光触媒機能が発揮されやすい。また、外壁材、板、パイプ、不織布等の表面に、酸化チタンエアロゲル粒子を含む塗料を塗着するとき、酸化チタンエアロゲル粒子の凝集又は塗布欠陥が抑制され、長期にわたり光触媒機能が発揮されやすい。
In general, titanium oxide airgel particles do not have good dispersibility in a resin or a solvent, and therefore, the uniformity of the coating film is low, and the photocatalytic function tends to be difficult to be exhibited.
On the other hand, the titanium oxide airgel particles having the organometallic compound bonded to the surface have good dispersibility in the resin or the solvent because they have a hydrocarbon group derived from the organometallic compound on the surface. Therefore, a nearly uniform coating film can be formed, and the titanium oxide airgel particles are efficiently exposed to light, and the photocatalytic function is easily exhibited. Further, when a paint containing titanium oxide airgel particles is applied to the surface of an outer wall material, a plate, a pipe, a non-woven fabric, etc., aggregation or coating defects of the titanium oxide airgel particles are suppressed, and the photocatalytic function is likely to be exhibited for a long period of time.
＜酸化チタンエアロゲル粒子の製造方法＞
本実施形態に係る酸化チタンエアロゲル粒子の製造方法は、特に制限はない。例えば、ゾルゲル法により酸化チタンを含む多孔質粒子を得て、この多孔質粒子を有機金属化合物により表面処理することにより得られる。この場合、表面処理した後に多孔質粒子を加熱処理して、加熱処理後の多孔質粒子を、本実施形態に係る酸化チタンエアロゲル粒子とすることが好ましい。
<Manufacturing method of titanium oxide airgel particles>
The method for producing titanium oxide airgel particles according to this embodiment is not particularly limited. For example, it is obtained by obtaining porous particles containing titanium oxide by a sol-gel method and surface-treating the porous particles with an organometallic compound. In this case, it is preferable that the porous particles are heat-treated after the surface treatment to obtain the heat-treated porous particles as the titanium oxide airgel particles according to the present embodiment.
以下、本実施形態に係る酸化チタンエアロゲル粒子の製造方法の形態例を説明する。 Hereinafter, an example of a method for producing titanium oxide airgel particles according to the present embodiment will be described.
酸化チタンエアロゲル粒子の製造方法は、少なくとも下記の（１）、（２）、（３）及び（４）を含むことが好ましい。
（１）酸化チタンを含む多孔質粒子をゾルゲル法により造粒し、前記多孔質粒子及び溶媒を含有する分散液を調製する工程（分散液調製工程）。
（２）超臨界二酸化炭素を用いて前記分散液から前記溶媒を除去する工程（溶媒除去工程）。
（３）前記溶媒を除去した後の前記多孔質粒子を、金属原子及び炭化水素基を有する金属化合物により表面処理する工程（表面処理工程）。好ましくは、前記溶媒を除去した後の前記多孔質粒子を、超臨界二酸化炭素中で、金属原子及び炭化水素基を有する金属化合物により表面処理する工程。
（４）前記表面処理した後の前記多孔質粒子を加熱処理する工程（加熱処理工程）。
The method for producing titanium oxide airgel particles preferably includes at least the following (1), (2), (3) and (4).
(1) A step of granulating porous particles containing titanium oxide by a sol-gel method to prepare a dispersion liquid containing the porous particles and a solvent (dispersion liquid preparation step).
(2) A step of removing the solvent from the dispersion liquid using supercritical carbon dioxide (solvent removal step).
(3) A step of surface-treating the porous particles after removing the solvent with a metal compound having a metal atom and a hydrocarbon group (surface treatment step). Preferably, the porous particles after removing the solvent are surface-treated with a metal compound having a metal atom and a hydrocarbon group in supercritical carbon dioxide.
(4) A step of heat-treating the porous particles after the surface treatment (heat treatment step).
［（１）分散液調製工程］
分散液調製工程は、例えば、チタンアルコキシドを材料にして、チタンアルコキシドの反応（加水分解及び縮合）を生じさせて酸化チタンを生成し、酸化チタンを含む多孔質粒子が溶媒に分散した分散液を得る工程である。
[(1) Dispersion liquid preparation step]
In the dispersion preparation step, for example, titanium alkoxide is used as a material to cause a reaction (hydrolysis and condensation) of titanium alkoxide to produce titanium oxide, and a dispersion in which porous particles containing titanium oxide are dispersed in a solvent is prepared. This is the process of obtaining.
分散液調製工程は、具体的には、例えば下記の工程とする。
アルコールにチタンアルコキシドを添加し、撹拌下、そこに酸水溶液を滴下してチタンアルコキシドを反応させて酸化チタンを生成し、酸化チタンを含む多孔質粒子がアルコールに分散した分散液（多孔質粒子分散液）を得る。
Specifically, the dispersion liquid preparation step is, for example, the following step.
Titanium alkoxide is added to alcohol, and an acid aqueous solution is dropped therein under stirring to react titanium alkoxide to produce titanium oxide, and a dispersion liquid in which porous particles containing titanium oxide are dispersed in alcohol (porous particle dispersion). Liquid).
ここで、分散液調整工程のチタンアルコキシド添加量により、多孔質粒子の一次粒子径を制御することができ、チタンアルコキシド添加量が多いほど多孔質粒子の一次粒子径が小さくなる。アルコールに対するチタンアルコキシドの質量比は、０．０４以上０．６５以下が好ましく、０．１以上０．５以下がより好ましい。 Here, the primary particle size of the porous particles can be controlled by the amount of titanium alkoxide added in the dispersion liquid adjusting step, and the larger the amount of titanium alkoxide added, the smaller the primary particle size of the porous particles. The mass ratio of titanium alkoxide to alcohol is preferably 0.04 or more and 0.65 or less, and more preferably 0.1 or more and 0.5 or less.
分散液調製工程に用いるチタンアルコキシドとしては、テトラメトキシチタン、テトラエトキシチタン、テトラプロポキシチタン、テトラブトキシチタン等のテトラアルコキシチタン、ジ−ｉプロポキシ・ビス（エチルアセテート）チタニウム、ジ−ｉ−プロポキシ・ビス（アセチルアセトナート）チタニウム等のアルコキシ基の一部をキレート化したアルコキシチタンキレート等が挙げられる。これらは、１種を単独で用いてもよいし、２種以上を併用してもよい。
なお、酸化チタンエアロゲル粒子は、ケイ素やアルミニウム等のチタン以外の金属元素を少量含んでも良い。この場合は、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等のテトラアルコキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン等のアルキルトリアルコキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン等のアルキルジアルコキシシラン、アルミニウムイソプロポキシド等のアルミニウムアルコキシド等を用いても良く、ケイ素元素を含む場合、ケイ素とチタンとの元素比Ｓｉ／Ｔｉが０〜０．０５の範囲で用いることができる。
Examples of the titanium alkoxy used in the dispersion preparation step include tetraalkoxytitanium such as tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, and tetrabutoxytitanium, di-ipropoxybis (ethylacetate) titanium, and di-i-propoxy. Examples thereof include an alkoxytitanium chelate obtained by chelating a part of an alkoxy group such as bis (acetylacetonate) titanium. These may be used alone or in combination of two or more.
The titanium oxide airgel particles may contain a small amount of metal elements other than titanium such as silicon and aluminum. In this case, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane, alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane and ethyltriethoxysilane, dimethyldimethoxysilane, Alkyldialkoxysilanes such as dimethyldiethoxysilane and aluminumalkoxides such as aluminumisopropoxide may be used, and when silicon elements are contained, the element ratio Si / Ti between silicon and titanium is in the range of 0 to 0.05. Can be used in.
分散液調製工程に用いるアルコールとしては、メタノール、エタノール、プロパノール、ブタノール等が挙げられる。これらは、１種を単独で用いてもよいし、２種以上を併用してもよい。 Examples of the alcohol used in the dispersion preparation step include methanol, ethanol, propanol, butanol and the like. These may be used alone or in combination of two or more.
分散液調製工程に用いる酸水溶液の酸としては、シュウ酸、酢酸、塩酸、硝酸等が挙げられる。酸水溶液の酸濃度は０．００１質量％以上１質量％以下が好ましく、０．００５質量％以上０．０１質量％以下がより好ましい。 Examples of the acid of the aqueous acid solution used in the dispersion preparation step include oxalic acid, acetic acid, hydrochloric acid, nitric acid and the like. The acid concentration of the aqueous acid solution is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.005% by mass or more and 0.01% by mass or less.
分散液調製工程おける酸水溶液の滴下量は、チタンアルコキシド１００質量部に対して、０．００１質量部以上０．１質量部以下が好ましい。 The amount of the aqueous acid solution dropped in the dispersion preparation step is preferably 0.001 part by mass or more and 0.1 part by mass or less with respect to 100 parts by mass of titanium alkoxide.
分散液調製工程によって得られる多孔質粒子分散液は、固形分濃度が１質量％以上３０質量％以下であることが好ましい。 The porous particle dispersion obtained in the dispersion preparation step preferably has a solid content concentration of 1% by mass or more and 30% by mass or less.
［（２）溶媒除去工程］
溶媒除去工程は、超臨界二酸化炭素を、多孔質粒子及び溶媒を含有する分散液に接触させて、溶媒を除去する工程である。超臨界二酸化炭素による溶媒除去処理は、加熱による溶媒除去処理に比べて、多孔質粒子の孔のつぶれや閉塞を起しにくい。溶媒除去工程が超臨界二酸化炭素によって溶媒を除去する工程であることにより、ＢＥＴ比表面積が１２０ｍ２／ｇ以上の酸化チタンエアロゲル粒子を得ることができる。
[(2) Solvent removal step]
The solvent removing step is a step of bringing the supercritical carbon dioxide into contact with the dispersion liquid containing the porous particles and the solvent to remove the solvent. The solvent removal treatment using supercritical carbon dioxide is less likely to cause the pores of the porous particles to be crushed or clogged than the solvent removal treatment by heating. Since the solvent removing step is a step of removing the solvent with supercritical carbon dioxide, titanium oxide airgel particles having a BET specific surface area of 120 m 2 / g or more can be obtained.
溶媒除去工程は、具体的には、例えば以下の操作によって行う。
密閉反応器に多孔質粒子分散液を投入し、次いで液化二酸化炭素を導入した後、密閉反応器を加熱すると共に高圧ポンプにより密閉反応器内を昇圧させ、密閉反応器内の二酸化炭素を超臨界状態とする。そして、密閉反応器に液化二酸化炭素を流入させ、密閉反応器から超臨界二酸化炭素を流出させることで、密閉反応器内において多孔質粒子分散液に超臨界二酸化炭素を流通させる。多孔質粒子分散液に超臨界二酸化炭素が流通する間に、溶媒が超臨界二酸化炭素に溶解し、密閉反応器外へ流出する超臨界二酸化炭素に同伴して溶媒が除去される。
Specifically, the solvent removing step is performed by, for example, the following operation.
After charging the porous particle dispersion into the closed reactor and then introducing liquefied carbon dioxide, the closed reactor is heated and the pressure inside the closed reactor is increased by a high-pressure pump to make the carbon dioxide in the closed reactor supercritical. Make it a state. Then, the liquefied carbon dioxide is made to flow into the closed reactor, and the supercritical carbon dioxide is discharged from the closed reactor, so that the supercritical carbon dioxide is circulated in the porous particle dispersion in the closed reactor. While the supercritical carbon dioxide flows through the porous particle dispersion, the solvent dissolves in the supercritical carbon dioxide, and the solvent is removed along with the supercritical carbon dioxide flowing out of the closed reactor.
上記の密閉反応器内の温度及び圧力は、二酸化炭素を超臨界状態にする温度及び圧力とする。二酸化炭素の臨界点が３１．１℃／７．３８ＭＰａであるところ、例えば、温度５０℃以上２００℃以下／圧力１０ＭＰａ以上３０ＭＰａ以下の温度及び圧力とする。 The temperature and pressure inside the closed reactor are the temperature and pressure that bring carbon dioxide into a supercritical state. Where the critical point of carbon dioxide is 31.1 ° C / 7.38 MPa, for example, the temperature and pressure are set to a temperature of 50 ° C. or higher and 200 ° C. or lower / a pressure of 10 MPa or higher and 30 MPa or lower.
［（３）表面処理工程］
表面処理工程は、金属原子及び炭化水素基を有する金属化合物（本開示において「有機金属化合物」ともいう。）と多孔質粒子の表面とを反応させる工程である。表面処理工程において、有機金属化合物中の反応性基（例えば、ハロゲノ基、アルコキシ基等の加水分解性基）と、多孔質粒子の表面に存在する反応性基（例えば、水酸基）とが反応し、多孔質粒子の表面処理がなされる。表面処理工程は、大気中または窒素雰囲気下で行なうことができるが、超臨界二酸化炭素中で表面処理工程を行うことにより、有機金属化合物が多孔質粒子の細孔の奥深くまで到達し、多孔質粒子の細孔の奥深くまで表面処理がなされることから、超臨界二酸化炭素中で表面処理を行なうことが好ましい。
[(3) Surface treatment process]
The surface treatment step is a step of reacting a metal compound having a metal atom and a hydrocarbon group (also referred to as “organic metal compound” in the present disclosure) with the surface of the porous particles. In the surface treatment step, the reactive group (for example, a hydrolyzable group such as a halogeno group or an alkoxy group) in the organic metal compound reacts with the reactive group (for example, a hydroxyl group) existing on the surface of the porous particles. , The surface of the porous particles is treated. The surface treatment step can be performed in the air or in a nitrogen atmosphere, but by performing the surface treatment step in supercritical carbon dioxide, the organic metal compound reaches deep into the pores of the porous particles and is porous. Since the surface treatment is performed deep into the pores of the particles, it is preferable to perform the surface treatment in supercritical carbon dioxide.
表面処理工程は、例えば、有機金属化合物と多孔質粒子とを、撹拌下、超臨界二酸化炭素中で混合し反応させる方法、有機金属化合物と溶媒とを混合してなる処理液を調製し、撹拌下、超臨界二酸化炭素中で多孔質粒子と処理液とを混合することで行われるが、多孔質粒子の細孔構造を保ち高いＢＥＴ比表面積を得るためには、（２）の溶媒除去工程の終了後に引き続き超臨界二酸化炭素中に有機金属化合物を投入し超臨界二酸化炭素中で有機金属化合物を多孔質粒子の表面と反応させる方法が好ましい。 In the surface treatment step, for example, a method in which an organic metal compound and porous particles are mixed and reacted in supercritical carbon dioxide under stirring, a treatment liquid prepared by mixing an organic metal compound and a solvent is prepared, and stirring is performed. Below, it is carried out by mixing the porous particles and the treatment liquid in supercritical carbon dioxide, but in order to maintain the pore structure of the porous particles and obtain a high BET specific surface area, the solvent removal step (2) The method of continuously putting the organic metal compound into the supercritical carbon dioxide and reacting the organic metal compound with the surface of the porous particles in the supercritical carbon dioxide is preferable.
表面処理工程の温度及び圧力は、二酸化炭素を超臨界状態にする温度及び圧力とする。例えば、温度５０℃以上２００℃以下／圧力１０ＭＰａ以上３０ＭＰａ以下の雰囲気で表面処理工程を行う。反応時間は、１０分間以上２４時間以下が好ましく、２０分間以上１２０分間以下がより好ましく、３０分間以上９０分間以下が更に好ましい。 The temperature and pressure of the surface treatment step shall be the temperature and pressure that bring carbon dioxide into a supercritical state. For example, the surface treatment step is performed in an atmosphere having a temperature of 50 ° C. or higher and 200 ° C. or lower / a pressure of 10 MPa or higher and 30 MPa or lower. The reaction time is preferably 10 minutes or more and 24 hours or less, more preferably 20 minutes or more and 120 minutes or less, and further preferably 30 minutes or more and 90 minutes or less.
表面処理に用いる有機金属化合物は、前述のとおりである。 The organometallic compound used for the surface treatment is as described above.
有機金属化合物と溶媒とを混合してなる処理液を用いる場合の溶媒としては、有機金属化合物と相溶性のあるものであれば特に制限はないが、メタノール、エタノール、プロパノール、ブタノール等のアルコール類；トルエン、酢酸エチル、アセトン等の有機溶剤が好ましく用いられる。 When a treatment liquid obtained by mixing an organic metal compound and a solvent is used, the solvent is not particularly limited as long as it is compatible with the organic metal compound, but alcohols such as methanol, ethanol, propanol and butanol are not particularly limited. An organic solvent such as toluene, ethyl acetate, or acetone is preferably used.
前記処理液において、有機金属化合物の量は、溶媒１００質量部に対して、１０質量部以上２００質量部以下が好ましく、２０質量部以上１８０質量部以下がより好ましく、５０質量部以上１５０質量部以下が更に好ましい。 In the treatment liquid, the amount of the organic metal compound is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 20 parts by mass or more and 180 parts by mass or less, and 50 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the solvent. The following is more preferable.
表面処理に用いる有機金属化合物の量は、多孔質粒子１００質量部に対して、１０質量部以上２００質量部以下が好ましく、２０質量部以上１８０質量部以下がより好ましく、３０質量部以上１５０質量部以下が更に好ましい。有機金属化合物の量を１０質量部以上にすると、可視光領域においても高い光触媒機能がより発現しやすく、また、分散性も高まる。有機金属化合物の量を２００質量部以下にすると、多孔質粒子の表面に存在する、有機金属化合物に由来する炭素量が過剰になることを抑え、余剰の炭素による光触媒機能の低下が抑制される。 The amount of the organic metal compound used for the surface treatment is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 20 parts by mass or more and 180 parts by mass or less, and 30 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the porous particles. Less than a portion is more preferable. When the amount of the organometallic compound is 10 parts by mass or more, a high photocatalytic function is more likely to be exhibited even in the visible light region, and the dispersibility is also enhanced. When the amount of the organometallic compound is 200 parts by mass or less, the amount of carbon derived from the organometallic compound present on the surface of the porous particles is suppressed from becoming excessive, and the deterioration of the photocatalytic function due to the excess carbon is suppressed. ..
表面処理後は、余剰の有機金属化合物、前記処理液の溶媒等の残渣を除去する目的で乾燥処理を行うことがよい。乾燥処理は、噴霧乾燥、棚段乾燥等の公知の方法を用いることができるが、超臨界二酸化炭素を用いて、多孔質粒子を含む分散液から溶媒を除去する工程が好ましく、表面処理工程終了後に引き続き、超臨界二酸化炭素中で超臨界二酸化炭素を流通させて溶媒を除去する工程が更に好ましい。具体的な操作は、前記（２）について述べた操作と同様でよい。 After the surface treatment, a drying treatment may be performed for the purpose of removing excess organometallic compounds, residues such as the solvent of the treatment liquid, and the like. As the drying treatment, known methods such as spray drying and shelf drying can be used, but a step of removing the solvent from the dispersion liquid containing the porous particles using supercritical carbon dioxide is preferable, and the surface treatment step is completed. Subsequently, a step of circulating supercritical carbon dioxide in supercritical carbon dioxide to remove the solvent is further preferable. The specific operation may be the same as the operation described in (2) above.
［（４）加熱処理工程］
加熱処理工程により、酸化チタンエアロゲル粒子の可視光における光触媒機能がより向上する。詳細な機序は不明であるが、表面および細孔内に結合している有機金属化合物が有する炭化水素基の一部が加熱処理により酸化または炭化されることによって、可視光に吸収を持つようになり、紫外光と共に可視光の吸収によっても光電荷分離機能が働くことで光触媒機能が発現すると考えられる。これは酸化チタンエアロゲル粒子が、可視吸収スペクトルにおいて波長４５０ｎｍ及び７５０ｎｍの各波長に吸収を持つことを示している。つまり、酸化チタンエアロゲル粒子の表面および細孔内に存在する酸化または炭化した炭化水素の一部または炭化した炭素により紫外光と共に可視光の光吸収によって選択的に電子を捕捉する作用が働く。これにより光吸収によって発生した電子と正孔が再結合する確率を低くしており、効率的に電荷の分離を促進し、この電荷分離の促進により酸化チタンエアロゲル粒子の可視光応答性が高まると推測される。
[(4) Heat treatment step]
The heat treatment step further improves the photocatalytic function of the titanium oxide airgel particles in visible light. Although the detailed mechanism is unknown, some of the hydrocarbon groups of the organic metal compounds bonded to the surface and the pores are oxidized or carbonized by heat treatment so that they have absorption in visible light. Therefore, it is considered that the photocatalytic function is exhibited by the photocharge separation function working by absorbing visible light together with ultraviolet light. This indicates that the titanium oxide airgel particles have absorption at wavelengths of 450 nm and 750 nm in the visible absorption spectrum. That is, a part of the oxidized or carbonized hydrocarbon present in the surface and pores of the titanium oxide airgel particles or the carbonized carbon acts to selectively capture electrons by absorbing visible light together with ultraviolet light. This lowers the probability that electrons and holes generated by light absorption will recombine, efficiently promotes charge separation, and this promotion of charge separation enhances the visible light responsiveness of titanium oxide airgel particles. Guessed.
加熱処理の温度は、光触媒機能の向上の観点から、１８０℃以上５００℃以下が好ましく、２００℃以上４５０℃以下がより好ましく、２５０℃以上４００℃以下が更に好ましい。加熱処理の時間は、光触媒機能の向上の観点から、１０分間以上２４時間以下が好ましく、２０分間以上３００分間以下がより好ましく、３０分間以上１２０分間以下が更に好ましい。 From the viewpoint of improving the photocatalytic function, the temperature of the heat treatment is preferably 180 ° C. or higher and 500 ° C. or lower, more preferably 200 ° C. or higher and 450 ° C. or lower, and further preferably 250 ° C. or higher and 400 ° C. or lower. From the viewpoint of improving the photocatalytic function, the heat treatment time is preferably 10 minutes or more and 24 hours or less, more preferably 20 minutes or more and 300 minutes or less, and further preferably 30 minutes or more and 120 minutes or less.
加熱処理の方法は、特に限定されず、例えば、電気炉、焼成炉（ローラーハースキルン、シャトルキルン等）、輻射式加熱炉、ホットプレート等による加熱；レーザー光、赤外線、ＵＶ、マイクロ波等による加熱；など公知の加熱方法を適用する。 The method of heat treatment is not particularly limited, and is, for example, heating by an electric furnace, a firing furnace (roller herring, shuttle kiln, etc.), a radiant heating furnace, a hot plate, etc .; by laser light, infrared rays, UV, microwaves, etc. Heating; A known heating method such as heating is applied.
以上の工程を経て、本実施形態に係る酸化チタンエアロゲル粒子が得られる。 Through the above steps, titanium oxide airgel particles according to the present embodiment can be obtained.
＜光触媒形成用組成物＞
本実施形態に係る光触媒形成用組成物は、本実施形態に係る酸化チタンエアロゲル粒子と、分散媒及びバインダーからなる群から選ばれた少なくとも１種の化合物とを含む。
<Composition for forming a photocatalyst>
The composition for forming a photocatalyst according to the present embodiment contains titanium oxide airgel particles according to the present embodiment and at least one compound selected from the group consisting of a dispersion medium and a binder.
本実施形態に係る光触媒形成用組成物の態様としては、例えば、本実施形態に係る酸化チタンエアロゲル粒子及び分散媒を含む分散液；本実施形態に係る酸化チタンエアロゲル粒子及び有機又は無機バインダーを含む組成物；などが挙げられる。分散液は、粘度が高いペースト状のものであってもよい。 Examples of the photocatalyst-forming composition according to the present embodiment include, for example, a dispersion liquid containing the titanium oxide airgel particles and the dispersion medium according to the present embodiment; the titanium oxide airgel particles and the organic or inorganic binder according to the present embodiment. Compositions; and the like. The dispersion liquid may be in the form of a paste having a high viscosity.
前記分散媒としては、水、有機溶媒等が好ましく用いられる。水としては、例えば、水道水、蒸留水、純水などが挙げられる。有機溶媒としては、特に制限はなく、例えば、炭化水素系溶媒、エステル系溶媒、エーテル系溶媒、ハロゲン系溶媒、アルコール系溶媒等が挙げられる。前記分散液は、分散安定性及び保存安定性の観点から、分散剤及び界面活性剤からなる群から選ばれた少なくとも１種の化合物を含有することが好ましい。分散剤及び界面活性剤としては、公知の化学物質が用いられる。分散液は、バインダーをエマルションとして含んでいてもよい。 As the dispersion medium, water, an organic solvent and the like are preferably used. Examples of water include tap water, distilled water, pure water and the like. The organic solvent is not particularly limited, and examples thereof include a hydrocarbon solvent, an ester solvent, an ether solvent, a halogen solvent, and an alcohol solvent. From the viewpoint of dispersion stability and storage stability, the dispersion liquid preferably contains at least one compound selected from the group consisting of dispersants and surfactants. Known chemical substances are used as the dispersant and the surfactant. The dispersion may contain a binder as an emulsion.
前記組成物に用いられるバインダーとしては、特に制限はないが、フッ素樹脂、シリコーン樹脂、ポリエステル樹脂、アクリル樹脂、スチレン樹脂、アクリロニトリル／スチレン共重合樹脂、アクリロニトリル／ブタジエン／スチレン共重合（ＡＢＳ）樹脂、エポキシ樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリアミン樹脂、ポリウレタン樹脂、ポリエーテル樹脂、ポリサルファイド樹脂、ポリフェノール樹脂、これらの複合物、これらをシリコーン変性又はハロゲン変性させた樹脂等の有機系バインダー；ガラス、セラミック、金属粉、セメント、石膏、珪藻土などの無機系バインダーが挙げられる。 The binder used in the composition is not particularly limited, but is a fluororesin, a silicone resin, a polyester resin, an acrylic resin, a styrene resin, an acrylonitrile / styrene copolymer resin, an acrylonitrile / butadiene / styrene copolymer (ABS) resin, and the like. Organic binders such as epoxy resin, polycarbonate resin, polyamide resin, polyamine resin, polyurethane resin, polyether resin, polysulfide resin, polyphenol resin, composites thereof, and resins obtained by silicone-modified or halogen-modified of these; glass, ceramic, Examples thereof include inorganic binders such as metal powder, cement, gypsum, and diatomaceous soil.
本実施形態に係る光触媒形成用組成物は、上記以外のその他の成分を含有してもよい。その他の成分としては、公知の添加剤が用いられ、例えば、助触媒、着色剤、充填剤、防腐剤、消泡剤、密着改良剤、増粘剤などが挙げられる。 The composition for forming a photocatalyst according to the present embodiment may contain other components other than the above. As other components, known additives are used, and examples thereof include co-catalysts, colorants, fillers, preservatives, defoamers, adhesion improvers, and thickeners.
本実施形態に係る光触媒形成用組成物は、本実施形態に係る酸化チタンエアロゲル粒子を１種単独で含んでいてもよいし、２種以上含んでいてもよい。 The composition for forming a photocatalyst according to the present embodiment may contain one kind of titanium oxide airgel particles according to the present embodiment alone, or may contain two or more kinds.
本実施形態に係る光触媒形成用組成物における本実施形態に係る酸化チタンエアロゲル粒子の含有量は、特に制限はなく、分散液、樹脂組成物等の各種態様、及び、所望の光触媒量等に応じて、適宜選択すればよい。 The content of the titanium oxide airgel particles according to the present embodiment in the photocatalyst forming composition according to the present embodiment is not particularly limited, and depends on various aspects such as a dispersion liquid and a resin composition, a desired photocatalyst amount, and the like. Then, it may be selected as appropriate.
本実施形態に係る光触媒形成用組成物を用いる光触媒又は光触媒を有する構造体の製造方法としては、特に制限はなく、公知の付与方法が用いられる。本実施形態に係る光触媒形成用組成物の付与方法としては、例えば、スピンコーティング法、ディップコーティング法、フローコーティング法、スプレーコーティング法、ロールコーティング法、刷毛塗り法、スポンジ塗り法、スクリーン印刷法、インクジェット印刷法などが挙げられる。 The method for producing a photocatalyst or a structure having a photocatalyst using the photocatalyst forming composition according to the present embodiment is not particularly limited, and a known application method is used. Examples of the method for applying the photocatalyst forming composition according to the present embodiment include a spin coating method, a dip coating method, a flow coating method, a spray coating method, a roll coating method, a brush coating method, a sponge coating method, and a screen printing method. Inkjet printing method and the like can be mentioned.
＜光触媒、構造体＞
本実施形態に係る光触媒は、本実施形態に係る酸化チタンエアロゲル粒子を含む、又は、本実施形態に係る酸化チタンエアロゲル粒子からなる。本実施形態に係る構造体は、本実施形態に係る酸化チタンエアロゲル粒子を有する。
<Photocatalyst, structure>
The photocatalyst according to the present embodiment contains the titanium oxide airgel particles according to the present embodiment, or is composed of the titanium oxide airgel particles according to the present embodiment. The structure according to the present embodiment has titanium oxide airgel particles according to the present embodiment.
本実施形態に係る光触媒は、本実施形態に係る酸化チタンエアロゲル粒子のみからなる光触媒であってもよいし、本実施形態に係る酸化チタンエアロゲル粒子に助触媒を混合した光触媒であっても、本実施形態に係る酸化チタンエアロゲル粒子を接着剤や粘着剤により所望の形状に固めた光触媒であってもよい。 The photocatalyst according to the present embodiment may be a photocatalyst composed of only the titanium oxide aerogel particles according to the present embodiment, or may be a photocatalyst obtained by mixing a co-catalyst with the titanium oxide aerogel particles according to the present embodiment. It may be a photocatalyst in which the titanium oxide aerogel particles according to the embodiment are hardened into a desired shape by an adhesive or a pressure-sensitive adhesive.
本実施形態に係る構造体は、光触媒として、本実施形態に係る酸化チタンエアロゲル粒子を有することが好ましい。本実施形態に係る構造体は、光触媒活性の観点から、本実施形態に係る酸化チタンエアロゲル粒子を少なくとも表面に有することが好ましい。 The structure according to the present embodiment preferably has titanium oxide airgel particles according to the present embodiment as a photocatalyst. From the viewpoint of photocatalytic activity, the structure according to the present embodiment preferably has titanium oxide airgel particles according to the present embodiment at least on the surface.
本実施形態に係る構造体は、基材表面の少なくとも一部に本実施形態に係る酸化チタンエアロゲル粒子を有する構造体であってもよいし、基材表面の少なくとも一部に本実施形態に係る光触媒形成用組成物を付与して形成された構造体であってもよい。該構造体において、本実施形態に係る光触媒形成用組成物を付与する量は、特に制限はなく、所望に応じて選択すればよい。 The structure according to the present embodiment may be a structure having titanium oxide aerogel particles according to the present embodiment on at least a part of the surface of the base material, or may be a structure having at least a part of the surface of the base material according to the present embodiment. It may be a structure formed by applying a composition for forming a photocatalyst. In the structure, the amount of the photocatalyst forming composition according to the present embodiment is not particularly limited and may be selected as desired.
本実施形態に係る構造体においては、基材表面に本実施形態に係る酸化チタンエアロゲル粒子が付着した状態であっても、固定化されていてもよいが、光触媒の耐久性の観点から、固定化されていることが好ましい。固定化方法は、特に制限はなく、公知の固定化方法が用いられる。 In the structure according to the present embodiment, the titanium oxide airgel particles according to the present embodiment may be attached to the surface of the base material or may be immobilized, but from the viewpoint of the durability of the photocatalyst, they are immobilized. It is preferable that it is made. The immobilization method is not particularly limited, and a known immobilization method is used.
本実施形態に用いられる基材は、無機材料、有機材料を問わず種々の材料が挙げられ、その形状も限定されない。基材の好ましい例としては、金属、セラミック、ガラス、プラスチック、ゴム、石、セメント、コンクリート、繊維、布帛、木、紙、これらの組合せ、これらの積層体、これらの表面に少なくとも一層の被膜を有する物品が挙げられる。用途の観点からみた基材の好ましい例としては、建材、外装材、窓枠、窓ガラス、鏡、テーブル、食器、カーテン、レンズ、プリズム、乗物の外装及び塗装、機械装置の外装、物品の外装、防塵カバー及び塗装、交通標識、各種表示装置、広告塔、道路用遮音壁、鉄道用遮音壁、橋梁、ガードレールの外装及び塗装、トンネル内装及び塗装、碍子、太陽電池カバー、太陽熱温水器集熱カバー、ポリマーフィルム、ポリマーシート、フィルター、屋内看板、屋外看板、車両用照明灯のカバー、屋外用照明器具、空気清浄器、浄水器、医療用器具、介護用品などが挙げられる。 Examples of the base material used in the present embodiment include various materials regardless of whether they are inorganic materials or organic materials, and their shapes are not limited. Preferred examples of substrates are metals, ceramics, glass, plastics, rubber, stones, cement, concrete, fibers, fabrics, wood, paper, combinations thereof, laminates thereof, and at least one layer of coating on their surfaces. The article to have is mentioned. Preferred examples of base materials from the viewpoint of application are building materials, exterior materials, window frames, windowpanes, mirrors, tables, tableware, curtains, lenses, prisms, vehicle exteriors and paints, mechanical equipment exteriors, and article exteriors. , Dustproof cover and paint, traffic signs, various display devices, advertising towers, road sound insulation walls, railway sound insulation walls, bridges, guard rail exterior and paint, tunnel interior and paint, glass, solar cell cover, solar water heater heat collector cover, Examples include polymer films, polymer sheets, filters, indoor signs, outdoor signs, vehicle lighting covers, outdoor lighting fixtures, air purifiers, water purifiers, medical appliances, nursing care products, and the like.
以下、実施例により発明の実施形態を詳細に説明するが、発明の実施形態は、これら実施例に何ら限定されるものではない。以下の説明において、特に断りのない限り、「部」はすべて質量基準である。 Hereinafter, embodiments of the invention will be described in detail with reference to Examples, but the embodiments of the invention are not limited to these Examples. In the following description, all "parts" are based on mass unless otherwise specified.
＜実施例１＞
［分散液調製工程］
反応容器にメタノール１１５．４部とテトラブトキシチタン１４．３部を仕込み混合した。混合液をマグネティックスターラーにより１００ｒｐｍで撹拌しながら、０．００９質量％シュウ酸水溶液７．５部を３０秒かけて滴下した。そのまま撹拌しながら３０分間保持し、分散液（１）を１３７．２部（固形分：３．４部、液相分：１３３．９部）得た。
<Example 1>
[Dispersion preparation process]
115.4 parts of methanol and 14.3 parts of tetrabutoxytitanium were charged and mixed in the reaction vessel. While stirring the mixed solution with a magnetic stirrer at 100 rpm, 7.5 parts of a 0.009 mass% oxalic acid aqueous solution was added dropwise over 30 seconds. The mixture was kept as it was with stirring for 30 minutes to obtain 137.2 parts (solid content: 3.4 parts, liquid phase content: 133.9 parts) of the dispersion liquid (1).
［溶媒除去工程］
反応槽に分散液（１）を１３７．２部投入し、８５ｒｐｍで撹拌しながらＣＯ２を入れて１５０℃／２０ＭＰａまで昇温昇圧した。そのまま撹拌しながらＣＯ２を流入及び流出させ、６０分かけて液相を１３２部除去した。
[Solvent removal step]
137.2 parts of the dispersion liquid (1) was put into the reaction vessel, CO 2 was added while stirring at 85 rpm, and the temperature was raised to 150 ° C./20 MPa. CO 2 was introduced and discharged while stirring as it was, and 132 parts of the liquid phase was removed over 60 minutes.
［表面処理工程］
液相を除去した後に残った固相に、イソブチルトリメトキシシラン３．４部とメタノール３．４部との混合物を５分かけて添加し、８５ｒｐｍで撹拌しながら１５０℃／２０ＭＰａのまま３０分間保持した。そのまま撹拌しながらＣＯ２を流入及び流出させ、３０分かけて液相を６．５部除去した。３０分かけて大気圧まで減圧し、粉を４．０部回収した。
[Surface treatment process]
A mixture of 3.4 parts of isobutyltrimethoxysilane and 3.4 parts of methanol was added to the solid phase remaining after removing the liquid phase over 5 minutes, and the mixture was stirred at 85 rpm for 30 minutes at 150 ° C./20 MPa. Retained. CO 2 was introduced and discharged while stirring as it was, and 6.5 parts of the liquid phase was removed over 30 minutes. The pressure was reduced to atmospheric pressure over 30 minutes, and 4.0 parts of the powder was recovered.
［加熱処理工程］
ＳＵＳ容器に粉を０．５部計量し、酸素濃度（体積％）を２０％に設定した電気炉で３８０℃、６０分間の加熱処理を行い、３０℃になるまで放冷し、粉（酸化チタンエアロゲル粒子）を０．５部回収した。
[Heat treatment process]
Weigh 0.5 parts of powder in a SUS container, heat-treat at 380 ° C for 60 minutes in an electric furnace set to an oxygen concentration (% by volume) of 20%, allow to cool to 30 ° C, and powder (oxidize). Titanium airgel particles) were recovered in 0.5 parts.
＜実施例２〜２１、比較例１Ａ〜７Ａ＞
表１〜表３に記載のとおりに材料又は処理条件を変更した以外は、実施例１と同様にして、各酸化チタンエアロゲル粒子を作製した。
<Examples 2 to 21, Comparative Examples 1A to 7A>
Titanium oxide airgel particles were prepared in the same manner as in Example 1 except that the materials or treatment conditions were changed as shown in Tables 1 to 3.
＜比較例１Ｂ＞
市販のアナターゼ型酸化チタン粒子（「ＳＳＰ−２０（堺化学工業社製）」）を、そのまま、酸化チタン粒子とした。
<Comparative Example 1B>
Commercially available anatase-type titanium oxide particles (“SSP-20 (manufactured by Sakai Chemical Industry Co., Ltd.)”) were used as they were as titanium oxide particles.
＜比較例２Ｂ＞
市販のアナターゼ型酸化チタン粒子（「ＳＳＰ−２０（堺化学工業社製）」）に対して、電気炉で３８０℃、１時間の加熱処理を行い、酸化チタン粒子を得た。
<Comparative Example 2B>
Commercially available anatase-type titanium oxide particles (“SSP-20 (manufactured by Sakai Chemical Industry Co., Ltd.)”) were heat-treated at 380 ° C. for 1 hour in an electric furnace to obtain titanium oxide particles.
＜比較例３Ｂ＞
市販のアナターゼ型酸化チタン粒子（「ＳＳＰ−２０（堺化学工業社製）」）をメタノールに分散した分散液に、酸化チタン粒子に対して３５質量％のヘキシルトリメトキシシランを滴下し、４０℃で１時間反応させた後、出口温度１２０℃で噴霧乾燥して乾燥粉体を得た。
<Comparative Example 3B>
35% by mass of hexyltrimethoxysilane with respect to the titanium oxide particles was added dropwise to a dispersion liquid in which commercially available anatase-type titanium oxide particles (“SSP-20 (manufactured by Sakai Chemical Industry Co., Ltd.)”) were dispersed in methanol, and the temperature was 40 ° C. After reacting with the above for 1 hour, it was spray-dried at an outlet temperature of 120 ° C. to obtain a dry powder.
＜粒子の物性の測定＞
各例で得られた粒子について、下記の測定方法に従って各物性を測定した。表１〜表４に、その結果を示す。表１〜表４中、ＧＳＤｖは粒子の体積粒度分布、「ＵＶ−Ｖｉｓ特性」は、波長３５０ｎｍの吸光度を１としたときの、波長４５０ｎｍ、波長６００ｎｍ及び波長７５０ｎｍそれぞれの吸光度である。
なお、一次粒子径、一次粒子径の凝集により形成される酸化チタンエアロゲル粒子の粒子径は、図１に示す粒子を対象とする粒子径とする。つまり、酸化チタンエアロゲル粒子の一次粒子径は、酸化チタンエアロゲル粒子を構成する粒子の粒径であり、酸化チタンエアロゲル粒子の粒径は、粒子が凝集した二次粒子の粒径である。
<Measurement of physical properties of particles>
The physical characteristics of the particles obtained in each example were measured according to the following measuring methods. The results are shown in Tables 1 to 4. In Tables 1 to 4, GSDv is the volume particle size distribution of the particles, and "UV-Vis characteristic" is the absorbance at a wavelength of 450 nm, a wavelength of 600 nm, and a wavelength of 750 nm when the absorbance at a wavelength of 350 nm is 1.
The particle size of the titanium oxide aerogel particles formed by the aggregation of the primary particle size and the primary particle size shall be the particle size of the particles shown in FIG. 1. That is, the primary particle size of the titanium oxide aerogel particles is the particle size of the particles constituting the titanium oxide aerogel particles, and the particle size of the titanium oxide aerogel particles is the particle size of the secondary particles in which the particles are aggregated.
［ＢＥＴ比表面積］
比表面積測定装置としてマウンテック社製「ＭａｃｓｏｒｂＨＭｍｏｄｅｌ−１２０１型」を使用し、５０ｍｇの試料に脱気のために３０℃／１２０分の前処理を行い、純度９９．９９％以上の窒素ガスを用いたＢＥＴ多点法にてＢＥＴ比表面積を求めた。
[BET specific surface area]
A Mountec "Macsorb HMmodel-1201" manufactured by Mountech was used as a specific surface area measuring device, and a 50 mg sample was pretreated at 30 ° C./120 minutes for degassing, and nitrogen gas having a purity of 99.99% or higher was used. The BET specific surface area was determined by the BET multipoint method.
［平均一次粒子径］
平均一次粒子径は、次のように測定した。体積平均粒径８μｍの樹脂粒子（スチレン−アクリル酸ブチル共重合体粒子（共重合比（質量比）＝８０：２０、重量平均分子量Ｍｗ＝１３万、ガラス転移温度Ｔｇ＝５９℃）１００質量部に対して、酸化チタンエアロゲル粒子１．０質量部を、サンプルミル（型式ＳＫ‐Ｍ ２型）（協立理工（株）製）を用いて１３０００ｒｐｍで２分間混合ブレンドした。樹脂粒子に酸化チタンエアロゲル粒子を分散させた後の酸化チタンエアロゲル粒子を、走査型電子顕微鏡ＳＥＭ（Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ）装置（（株）日立製作所製：Ｓ−４１００）により観察して画像を撮影し、この画像を画像解析装置（ＬＵＺＥＸＩＩＩ、（株）ニレコ製）に取り込み、一次粒子の画像解析によって粒子ごとの面積を測定し、この面積値から円相当径を算出し、その平均を平均一次粒子径とする。なお、電子顕微鏡は一次粒子が画像解析出来る倍率に調整し、一次粒子１０から５０個程度を解析し、平均一次粒子径が求められる。一次粒子径の判定は、図１に示すように凝集する酸化チタンエアロゲル粒子を形成する粒子を一次粒子と定義し、画像解析する。
[Average primary particle size]
The average primary particle size was measured as follows. 100 parts by mass of resin particles with a volume average particle size of 8 μm (styrene-butyl acrylate copolymer particles (copolymerization ratio (mass ratio) = 80:20, weight average molecular weight Mw = 130,000, glass transition temperature Tg = 59 ° C.) 1. The titanium oxide aerogel particles after the aerogel particles are dispersed are observed by a scanning electron microscope SEM (Scanning Electron Masscope) device (manufactured by Hitachi, Ltd .: S-4100), and an image is taken. It is taken into an analyzer (LUZEXIII, manufactured by Nireco Co., Ltd.), the area of each particle is measured by image analysis of the primary particles, the equivalent circle diameter is calculated from this area value, and the average is taken as the average primary particle diameter. , The electron microscope adjusts the magnification so that the primary particles can analyze the image, analyzes about 10 to 50 primary particles, and the average primary particle size is obtained. The determination of the primary particle size is the aggregation oxidation as shown in FIG. The particles that form the titanium aerogel particles are defined as primary particles and image analysis is performed.
［体積平均粒子径］
体積平均粒子径は、次のように測定した。体積平均粒径８μｍの樹脂粒子（スチレン−アクリル酸ブチル共重合体粒子（共重合比（質量比）＝８０：２０、重量平均分子量Ｍｗ＝１３万、ガラス転移温度Ｔｇ＝５９℃）１００質量部に対して、酸化チタンエアロゲル粒子１．０質量部を、サンプルミル（型式ＳＫ‐Ｍ ２型）（協立理工（株）製）を用いて１３０００ｒｐｍで２分間混合ブレンドした。ブレンド後の酸化チタン含有樹脂粒子を、ビーカーに０．１ｇを入れ、陰イオン性界面活性剤 （テイカ株式会社製、テイカパワーＢＮ２０６０）をイオン交換水にて１２％希釈した界面活性剤水溶液１．５ｇを添加し、粒子を充分ぬらした後、純水５ｇを添加、続いて超音波分散機で３０分間分散した後、５Ｃろ紙にて樹脂粒子を除去し、酸化チタンエアロゲル粒子分散液を得た。ナノトラックＵＰＡ-ＳＴ（マイクロトラック・ベル社製 動的光産卵式粒度測定装置）により測定して、酸化チタンエアロゲル粒子分散液中の酸化チタンエアロゲル粒子の体積平均粒子径を求めた。
具体的には、粒度分布を分割された粒度範囲（チャンネル）に対し、個々の粒子の体積について小径側から累積分布を描き、累積５０％となる体積平均粒径（粒径Ｄ５０ｖ）として求めた。
[Volume average particle size]
The volume average particle size was measured as follows. 100 parts by mass of resin particles with a volume average particle size of 8 μm (styrene-butyl acrylate copolymer particles (copolymerization ratio (mass ratio) = 80:20, weight average molecular weight Mw = 130,000, glass transition temperature Tg = 59 ° C.) 1. 0.1 g of the contained resin particles was placed in a beaker, and 1.5 g of a surfactant aqueous solution obtained by diluting an anionic surfactant (Taika Power BN2060 manufactured by Teika Co., Ltd.) by 12% with ion-exchanged water was added. After sufficiently wetting the particles, 5 g of pure water was added, and then the particles were dispersed for 30 minutes with an ultrasonic disperser, and then the resin particles were removed with a 5C filter paper to obtain a titanium oxide aerogel particle dispersion liquid. The volume average particle size of the titanium oxide aerogel particles in the titanium oxide aerogel particle dispersion was determined by measurement with ST (dynamic photo-spawning particle size measuring device manufactured by Microtrac Bell).
Specifically, the particle size distribution was obtained by drawing a cumulative distribution from the small diameter side for the volume of each particle with respect to the divided particle size range (channel), and obtaining the volume average particle size (particle size D50v) to be a cumulative 50%. ..
［体積粒度分布］
体積粒度分布は、次のように測定した。体積粒度分布の測定は、体積平均粒子径の測定同様に測定し、粒度分布を分割された粒度範囲（チャンネル）に対し、個々の粒子の体積について小径側から累積分布を描き、累積９０％となる粒径Ｄ９０ｖを、累積１０％となる粒径Ｄ１０ｖで除した値の平方根を体積粒度分布（ＧＳＤｖ）と定義する。すなわち、体積粒度分布（ＧＳＤｖ）＝（Ｄ９０ｖ/Ｄ１０ｖ）０．５である。
[Volume particle size distribution]
The volume particle size distribution was measured as follows. The volume particle size distribution is measured in the same way as the volume average particle size measurement, and the cumulative distribution is drawn from the small diameter side for the volume of each particle for the divided particle size range (channel), and the cumulative total is 90%. The square root of the value obtained by dividing the particle size D90v obtained by dividing the particle size D90v by the cumulative particle size D10v is defined as the volume particle size distribution (GSDv). That is, the volume particle size distribution (GSDv) = (D90v / D10v) 0.5 .
［紫外可視吸収スペクトル］
各例で得られた粒子をテトラヒドロフランに分散させた後、ガラス基板上に塗布し、大気中、２４℃で乾燥させた。分光光度計Ｕ−４１００（日立ハイテクノロジーズ社製）を使用し、スキャンスピード：６００ｎｍ、スリット幅：２ｎｍ、サンプリング間隔：１ｎｍに設定して、拡散反射配置で、波長２００ｎｍ乃至９００ｎｍの範囲の拡散反射スペクトルを測定した。拡散反射スペクトルから、Kubelka-Munk変換により理論的に各波長における吸光度を求め、紫外可視吸収スペクトルを得た。
[Ultraviolet-visible absorption spectrum]
The particles obtained in each example were dispersed in tetrahydrofuran, coated on a glass substrate, and dried in the air at 24 ° C. Using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), the scan speed is set to 600 nm, the slit width is set to 2 nm, and the sampling interval is set to 1 nm. The spectrum was measured. From the diffuse reflection spectrum, the absorbance at each wavelength was theoretically obtained by Kubelka-Munk conversion, and an ultraviolet-visible absorption spectrum was obtained.
実施例１〜２１の酸化チタンエアロゲル粒子は、波長４００ｎｍ以上８００ｎｍ以下の全範囲に吸収を有していた。 The titanium oxide airgel particles of Examples 1 to 21 had absorption in the entire range of a wavelength of 400 nm or more and 800 nm or less.
＜粒子の性能評価＞
［ガス吸着性とガス分解性］
各例で得られた粒子の活性として、下記のとおり、ガス吸着性と、可視光照射によるガス分解性とを評価した。表１に、その結果を示す。
<Evaluation of particle performance>
[Gas adsorption and gas decomposition]
As the activity of the particles obtained in each example, the gas adsorptivity and the gas decomposability by visible light irradiation were evaluated as follows. Table 1 shows the results.
各例で得られた粒子を固形分濃度が４質量％になるように、メタノールに分散させた。その分散液を顕微鏡用ガラスプレートの半分（面積１０ｃｍ２）に０．２５ｇ塗布した後、充分に乾燥し、ガラスプレートの表面（半分）に均一に粒子を付着させた試験片を作製した。試験片は、各例の粒子ごとに２つずつ作製した。 The particles obtained in each example were dispersed in methanol so that the solid content concentration was 4% by mass. 0.25 g of the dispersion was applied to half of the glass plate for a microscope (area 10 cm 2 ) and then sufficiently dried to prepare a test piece in which particles were uniformly adhered to the surface (half) of the glass plate. Two test pieces were prepared for each particle of each example.
試験片を作製後ただちに容量１Ｌの１つ口コック付きテドラーバックに入れ（テドラーバック１つにつき試験片を１つ入れた。）、テドラーバック内の空気を押し出し密封した後、塗布面を上にして暗所に置き、性能評価試験まで保管した。 Immediately after making the test piece, put it in a tedler bag with a one-mouth cock with a capacity of 1 L (one test piece was put in each tedler bag), extrude the air inside the tedler bag to seal it, and then put it in a dark place with the coating surface facing up. And stored until the performance evaluation test.
性能評価試験は、以下の手順で行った。
先ず、試験片入りテドラーバックのコックから内部の残存エアーを吸引器で全て排出し、次いで、１００ｐｐｍ濃度のアンモニアガスを８００ｍｌ注入した。次いで、同種２つの、試験片入りテドラーバックの一方には、波長４００ｎｍ以上８００ｎｍ以下の可視光を照射する発光ダイオード（ＬＥＤ）を使用して可視光（試験片表面で６，０００ＬＸ（ルクス））を連続照射した。同種２つの、試験片入りテドラーバックのもう一方は、光の当たらない暗箱に入れ１時間保管した。
可視光１時間連続照射後の試験片入りテドラーバック、暗箱で１時間保管した試験片入りテドラーバック、それぞれのテドラーバック内のアンモニアガス濃度を、検知管（ガステック社製）を用いて測定した。そして、下記の式から、アンモニアガス吸着性の指標ΔＡと、可視光照射によるアンモニアガス分解率ΔＳとを求めた。
The performance evaluation test was carried out according to the following procedure.
First, all the residual air inside was discharged from the cock of the tedler bag containing the test piece with a suction device, and then 800 ml of ammonia gas having a concentration of 100 ppm was injected. Next, visible light (6,000 LX (lux) on the surface of the test piece) is applied to one of the two tedler bags containing the test piece of the same type using a light emitting diode (LED) that irradiates visible light with a wavelength of 400 nm or more and 800 nm or less. Continuous irradiation was performed. The other of the two test pieces of the same type, the tedler bag containing the test piece, was placed in a dark box not exposed to light and stored for 1 hour.
The ammonia gas concentration in each of the tedler bag containing a test piece after continuous irradiation with visible light for 1 hour, the tedler bag containing a test piece stored in a dark box for 1 hour, and the ammonia gas concentration in each tedler bag was measured using a detector tube (manufactured by Gastec). Then, the index ΔA of the ammonia gas adsorption property and the ammonia gas decomposition rate ΔS by irradiation with visible light were obtained from the following formulas.
・Ｓ１＝可視光１時間連続照射後のテドラーバック内のアンモニアガス濃度（ｐｐｍ）
・Ｓ２＝暗箱で１時間保管した後のテドラーバック内のアンモニアガス濃度（ｐｐｍ）
・アンモニアガス吸着性の指標ΔＡ（ｐｐｍ）＝１００−Ｓ２
・アンモニアガス分解率ΔＳ（％）＝（Ｓ２−Ｓ１）÷Ｓ２×１００
-S1 = Ammonia gas concentration (ppm) in the tedler bag after continuous irradiation with visible light for 1 hour.
・ S2 = Ammonia gas concentration (ppm) in the tedler bag after storage in a dark box for 1 hour
-Ammonia gas adsorption index ΔA (ppm) = 100-S2
Ammonia gas decomposition rate ΔS (%) = (S2-S1) ÷ S2 × 100
上記の値から、ガス吸着性とガス分解性を下記のとおり評価した。 From the above values, the gas adsorptivity and gas decomposability were evaluated as follows.
−ガス吸着性−
Ｇ１（◎）：９０≦ΔＡ、吸着性が非常に良好。
Ｇ２（○）：７０≦ΔＡ＜９０、吸着性が良好。
Ｇ３（△）：５０≦ΔＡ＜７０、吸着性がやや良好。
Ｇ４（×）：ΔＡ＜５０、吸着性が不良。
-Gas adsorption-
G1 (◎): 90 ≦ ΔA, very good adsorptivity.
G2 (◯): 70 ≦ ΔA <90, good adsorptivity.
G3 (Δ): 50 ≦ ΔA <70, slightly good adsorptivity.
G4 (×): ΔA <50, poor adsorptivity.
−ガス分解性−
Ｇ１（◎）：３０≦ΔＳ、分解性が非常に良好。
Ｇ２（○）：１５≦ΔＳ＜３０、分解性が良好。
Ｇ３（△）：５≦ΔＳ＜１５、分解性がやや良好。
Ｇ４（×）：ΔＳ＜５、分解性が不良。
-Gas degradability-
G1 (◎): 30 ≦ ΔS, very good degradability.
G2 (◯): 15 ≦ ΔS <30, good degradability.
G3 (Δ): 5 ≦ ΔS <15, slightly good in decomposability.
G4 (×): ΔS <5, poor decomposability.
［粗大粒子の量］
目開き２０μｍの篩の重量を０．０１ｇ単位まで精密計量し、酸化チタンエアロゲル粒子１．００ｇを集塵機で吸引しながら篩を通過させた。その際、網上の凝集物を刷毛により解しながら篩を通過させ、篩上に残った強固な酸化チタンエアロゲル粒子量を粗大粒子量として測定した。
粗大粒子指数（％）＝（吸引後の篩の重量−吸引前の篩の重量）/１．０×１００
−粗大粒子指数−
Ｇ１（○）：２０μｍ以上が１％以下
Ｇ２（△）：２０μｍ以上が５％以下
Ｇ３（×）：２０μｍ以上が５％超
[Amount of coarse particles]
The weight of the sieve having a mesh size of 20 μm was precisely weighed to the unit of 0.01 g, and 1.00 g of titanium oxide airgel particles were passed through the sieve while being sucked by a dust collector. At that time, the agglomerates on the net were passed through the sieve while being broken by a brush, and the amount of strong titanium oxide airgel particles remaining on the sieve was measured as the amount of coarse particles.
Coarse particle index (%) = (weight of sieve after suction-weight of sieve before suction) /1.0 × 100
-Coarse particle index-
G1 (○): 20 μm or more is 1% or less G2 (Δ): 20 μm or more is 5% or less G3 (×): 20 μm or more is more than 5%
表１〜表４に示した性能評価の結果から、本実施例は、比較例（ただし、比較例６Ａを除く）に比べて、可視光領域において光触媒活性（ガス吸着性、ガス分解性）に優れることがわかる。
また、本実施例は、比較例６Ａに比べ、粗大粒子量を少なくしつつ、かつ可視光領域において光触媒活性（ガス吸着性、ガス分解性）にも優れることもわかる。
分散性が確保されていることがわかる。
From the results of the performance evaluations shown in Tables 1 to 4, this example has a photocatalytic activity (gas adsorptivity, gas decomposability) in the visible light region as compared with the comparative example (however, the comparative example 6A is excluded). It turns out to be excellent.
It can also be seen that this example is superior in photocatalytic activity (gas adsorptivity, gas decomposability) in the visible light region while reducing the amount of coarse particles as compared with Comparative Example 6A.
It can be seen that the dispersibility is ensured.
Claims (14)
ＢＥＴ比表面積が、１５０ｍ２／ｇ以上１０００ｍ２／ｇ以下であり、
可視吸収スペクトルにおいて波長４５０ｎｍ及び７５０ｎｍに吸収を持つ、
酸化チタンエアロゲル粒子。 A metal compound having a metal atom and a hydrocarbon group is bonded to the surface via an oxygen atom, and the metal compound is bonded to the surface.
The BET specific surface area is 150 m 2 / g or more and 1000 m 2 / g or less.
Has absorption at wavelengths of 450 nm and 750 nm in the visible absorption spectrum.
Titanium oxide airgel particles.
ＢＥＴ比表面積が、１２０ｍ ２ ／ｇ以上１０００ｍ ２ ／ｇ以下であり、
可視吸収スペクトルにおいて波長４５０ｎｍ及び７５０ｎｍに吸収を持ち、
一次粒子が凝集した凝集粒子であり、
平均一次粒子径が７８ｎｍ以上１１０ｎｍ以下である酸化チタンエアロゲル粒子。 A metal compound having a metal atom and a hydrocarbon group is bonded to the surface via an oxygen atom, and the metal compound is bonded to the surface.
The BET specific surface area is 120 m 2 / g or more and 1000 m 2 / g or less.
Has absorption at wavelengths of 450 nm and 750 nm in the visible absorption spectrum,
Aggregated particles in which primary particles are aggregated,
Titanium oxide airgel particles having an average primary particle size of 78 nm or more and 110 nm or less.
超臨界二酸化炭素を用いて前記分散液から前記溶媒を除去する工程と、
前記溶媒を除去した後の前記多孔質粒子を、超臨界二酸化炭素中で、金属原子及び炭化水素基を有する金属化合物により表面処理する工程と、
前記表面処理した後の前記多孔質粒子を加熱処理する工程と、
を含む、請求項１〜請求項１０のいずれか１項に記載の酸化チタンエアロゲル粒子の製造方法。 A step of granulating porous particles containing titanium oxide by a sol-gel method to prepare a dispersion liquid containing the porous particles and a solvent, and
The step of removing the solvent from the dispersion liquid using supercritical carbon dioxide, and
A step of surface-treating the porous particles after removing the solvent with a metal compound having a metal atom and a hydrocarbon group in supercritical carbon dioxide.
The step of heat-treating the porous particles after the surface treatment and
The method for producing titanium oxide airgel particles according to any one of claims 1 to 10, further comprising.
分散媒及びバインダーからなる群から選ばれた少なくとも１種の化合物と、
を含む光触媒形成用組成物。 The titanium oxide airgel particles according to any one of claims 1 to 10.
At least one compound selected from the group consisting of a dispersion medium and a binder, and
A composition for forming a photocatalyst containing.
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