JP2022017948A - Metal oxide fiber aggregate and manufacturing method thereof and catalyst constituted of the metal oxide fiber aggregate - Google Patents
Metal oxide fiber aggregate and manufacturing method thereof and catalyst constituted of the metal oxide fiber aggregate Download PDFInfo
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- JP2022017948A JP2022017948A JP2020120819A JP2020120819A JP2022017948A JP 2022017948 A JP2022017948 A JP 2022017948A JP 2020120819 A JP2020120819 A JP 2020120819A JP 2020120819 A JP2020120819 A JP 2020120819A JP 2022017948 A JP2022017948 A JP 2022017948A
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- Prior art keywords
- metal oxide
- oxide fiber
- fiber aggregate
- spinning
- aggregate
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- 239000000835 fiber Substances 0.000 title claims abstract description 377
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 353
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 353
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 128
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 64
- 238000009987 spinning Methods 0.000 claims description 103
- 239000007788 liquid Substances 0.000 claims description 62
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 238000010304 firing Methods 0.000 claims description 23
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 44
- 239000002243 precursor Substances 0.000 description 44
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- 238000002360 preparation method Methods 0.000 description 31
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
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- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
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- 239000000975 dye Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 150000002823 nitrates Chemical class 0.000 description 2
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
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- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
本発明は、少なくとも２種類の金属酸化物繊維を含む、金属酸化物繊維集合体及びその製造方法並びに前記金属酸化物繊維集合体から構成された触媒に関する。 The present invention relates to a metal oxide fiber aggregate containing at least two types of metal oxide fibers, a method for producing the same, and a catalyst composed of the metal oxide fiber aggregate.
金属酸化物繊維は、繊維形状であることで高い比表面積を有することから、触媒やフィルタなどを構成する材料として好適に使用できることが知られている。 It is known that the metal oxide fiber can be suitably used as a material constituting a catalyst, a filter, or the like because it has a high specific surface area due to its fiber shape.
このような金属酸化物繊維は、例えば、特開２０１４－８０７００号公報（特許文献１）に開示されている。また、非特許文献１には、メタンからエチレンやプロピレンを合成する触媒用途に用いることができる酸化ランタンと酸化セリウムから構成された金属酸化物繊維が開示されている。 Such metal oxide fibers are disclosed in, for example, Japanese Patent Application Laid-Open No. 2014-80700 (Patent Document 1). Further, Non-Patent Document 1 discloses a metal oxide fiber composed of lanthanum oxide and cerium oxide, which can be used as a catalyst for synthesizing ethylene or propylene from methane.
しかしながら、特許文献１、及び非特許文献１に開示されている金属酸化物繊維など、金属酸化物繊維の多くは柔軟性に劣る、及び／又は、脆いという問題を抱えており、そのため、金属酸化物繊維の強度が低く、金属酸化物繊維から構成された金属酸化物繊維集合体の形状が崩れる形崩れを起こすことがあった。 However, many metal oxide fibers such as the metal oxide fibers disclosed in Patent Document 1 and Non-Patent Document 1 have a problem of inferior flexibility and / or brittleness, and therefore, metal oxidation The strength of the physical fibers was low, and the shape of the metal oxide fiber aggregate composed of the metal oxide fibers was sometimes deformed.
本発明はこのような状況下においてなされたものであり、形崩れを起こしにくい金属酸化物繊維集合体を提供することを目的とする。 The present invention has been made under such circumstances, and an object of the present invention is to provide a metal oxide fiber aggregate that does not easily lose its shape.
本発明の請求項１に係る発明は、「シリカを主体とする金属酸化物繊維Ａと、シリカ以外の金属酸化物を主体とする金属酸化物繊維Ｂを含む、金属酸化物繊維集合体。」である。 The invention according to claim 1 of the present invention is "a metal oxide fiber aggregate containing a metal oxide fiber A mainly composed of silica and a metal oxide fiber B mainly composed of a metal oxide other than silica." Is.
本発明の請求項２に係る発明は、「金属酸化物繊維Ａと金属酸化物繊維Ｂの合計量に対する金属酸化物繊維Ａの質量比が、１０ｍａｓｓ％以上（１００ｍａｓｓ％を除く）である、請求項１に記載の金属酸化物繊維集合体。」である。 According to the second aspect of the present invention, "the mass ratio of the metal oxide fiber A to the total amount of the metal oxide fiber A and the metal oxide fiber B is 10 mass% or more (excluding 100 mass%). Item 1. The metal oxide fiber aggregate according to Item 1. ”.
本発明の請求項３に係る発明は、「金属酸化物繊維Ｂが、酸化ランタン、酸化セリウム、アルミナ、チタニア、ガドリニウムとセリウムの複合酸化物、リチウムとバナジウムの複合酸化物のうち少なくとも１つを含む、請求項１又は２に記載の金属酸化物繊維集合体。」である。 In the invention according to claim 3 of the present invention, "the metal oxide fiber B contains at least one of lanthanum oxide, cerium oxide, alumina, titania, a composite oxide of gadrinium and cerium, and a composite oxide of lithium and vanadium. The metal oxide fiber aggregate according to claim 1 or 2. ”.
本発明の請求項４に係る発明は、「請求項３に記載の金属酸化物繊維集合体を含む、触媒。」である。 The invention according to claim 4 of the present invention is "a catalyst containing the metal oxide fiber aggregate according to claim 3.".
本発明の請求項５に係る発明は、「（ｉ）ケイ素を含む物質を含む紡糸液ａと、ケイ素以外の金属を含む物質を含む紡糸液ｂを調製する工程、（ｉｉ）紡糸液ａを紡糸し焼成することで、シリカを主体とする金属酸化物繊維Ａを調製する工程、（ｉｉｉ）紡糸液ｂを紡糸し焼成することで、シリカ以外の金属酸化物を主体とする金属酸化物繊維Ｂを調製する工程、（ｉｖ）金属酸化物繊維Ａと金属酸化物繊維Ｂを混合し、金属酸化物繊維集合体を調製する工程、を含む、請求項１～３のいずれか１項に記載の金属酸化物繊維集合体の製造方法。」である。 The invention according to claim 5 of the present invention describes "(i) a step of preparing a spinning liquid a containing a substance containing silicon and a spinning liquid b containing a substance other than a metal other than silicon, (ii) a spinning liquid a. A step of preparing a metal oxide fiber A mainly composed of silica by spinning and firing, and (iii) a metal oxide fiber mainly composed of a metal oxide other than silica by spinning and firing the spinning liquid b. The step according to any one of claims 1 to 3, further comprising a step of preparing B, and (iv) a step of mixing the metal oxide fiber A and the metal oxide fiber B to prepare a metal oxide fiber aggregate. A method for producing an aggregate of metal oxide fibers. ”.
本発明の請求項１に係る金属酸化物繊維集合体は、強度が比較的高いシリカを主体とする金属酸化物繊維Ａを含んでいることにより、シリカ以外の金属酸化物を主体とする金属酸化物繊維Ｂのみから構成された金属酸化物繊維集合体と比べて、形崩れを起こしにくい金属酸化物繊維集合体を実現できる。 The metal oxide fiber aggregate according to claim 1 of the present invention contains a metal oxide fiber A mainly composed of silica having a relatively high strength, and thus metal oxidation mainly composed of a metal oxide other than silica. It is possible to realize a metal oxide fiber aggregate that is less likely to lose its shape as compared with a metal oxide fiber aggregate composed of only the material fiber B.
本発明の請求項２に係る金属酸化物繊維集合体は、金属酸化物繊維Ａと金属酸化物繊維Ｂの合計量に対する金属酸化物繊維Ａの質量比が、１０ｍａｓｓ％以上（１００ｍａｓｓ％を除く）であることにより、形崩れを起こしにくい金属酸化物繊維集合体を実現できる。 In the metal oxide fiber aggregate according to claim 2 of the present invention, the mass ratio of the metal oxide fiber A to the total amount of the metal oxide fiber A and the metal oxide fiber B is 10 mass% or more (excluding 100 mass%). Therefore, it is possible to realize a metal oxide fiber aggregate that does not easily lose its shape.
本発明の請求項３に係る金属酸化物繊維集合体は、金属酸化物繊維Ｂが、触媒作用を示す金属酸化物を含むことから、触媒用途に適した金属酸化物繊維集合体である。 The metal oxide fiber aggregate according to claim 3 of the present invention is a metal oxide fiber aggregate suitable for catalytic use because the metal oxide fiber B contains a metal oxide exhibiting a catalytic action.
本発明の請求項４に係る触媒は、形崩れを起こしにくい金属酸化物繊維集合体を含むことから、形崩れを起こしにくい触媒である。 The catalyst according to claim 4 of the present invention is a catalyst that does not easily lose its shape because it contains a metal oxide fiber aggregate that does not easily lose its shape.
本発明の請求項５に係る金属酸化物繊維集合体の製造方法は、強度が比較的高いシリカを主体とする金属酸化物Ａを混合することにより、形崩れを起こしにくい金属酸化物繊維集合体を製造できる方法である。 The method for producing a metal oxide fiber aggregate according to claim 5 of the present invention is a metal oxide fiber aggregate that does not easily lose its shape by mixing a metal oxide A mainly composed of silica having a relatively high strength. Is a method that can be manufactured.
本発明の金属酸化物繊維集合体は、シリカを主体とする金属酸化物繊維Ａを含む。なお、本発明における「主体とする」とは、５０ｍａｓｓ％以上のことをいう。金属酸化物繊維Ａに含まれるシリカの割合は、大きければ大きいほど、より金属酸化物繊維Ａの強度が高くなり、また、より金属酸化物繊維集合体の強度が高くなることから、金属酸化物繊維Ａに含まれるシリカの割合は、８０ｍａｓｓ％以上がより好ましく、９０ｍａｓｓ％以上が更に好ましく、１００ｍａｓｓ％が最も好ましい。なお、金属酸化物繊維Ａには、シリカの他に、染料などの有機成分や、ヒドロキシアパタイトやシリカ以外の金属酸化物などの無機成分を含有することができる。 The metal oxide fiber aggregate of the present invention contains the metal oxide fiber A mainly composed of silica. The term "mainly" in the present invention means 50 mass% or more. The larger the proportion of silica contained in the metal oxide fiber A, the higher the strength of the metal oxide fiber A and the higher the strength of the metal oxide fiber aggregate. Therefore, the metal oxide The ratio of silica contained in the fiber A is more preferably 80 mass% or more, further preferably 90 mass% or more, and most preferably 100 mass%. In addition to silica, the metal oxide fiber A can contain an organic component such as a dye and an inorganic component such as a metal oxide other than hydroxyapatite or silica.
金属酸化物繊維Ａの平均繊維径は、細ければ細いほど、厚さが薄く、近年の軽薄短小化の要望に合う金属酸化物繊維集合体を提供しやすいため、平均繊維径は１０μｍ以下であるのが好ましく、３μｍ以下であるのがより好ましく、２μｍ以下であるのが更に好ましい。一方、平均繊維径が細すぎると、金属酸化物繊維集合体の機械的強度が低下するおそれがあることから、０．１μｍ以上が適当である。なお、「平均繊維径」は、金属酸化物繊維５０点における繊維径の算術平均値をいい、「繊維径」は、金属酸化物繊維の断面を撮影した５０～５０００倍の電子顕微鏡写真を基に測定した、金属酸化物繊維の直径をいう。金属酸化物繊維Ａは繊維断面が円形でない異形断面であってもよく、異形断面の金属酸化物繊維Ａの繊維径の測定方法は、異形断面の断面積を計測し、その断面積を有する円の直径を繊維径とみなす。異形断面の金属酸化物繊維Ａの断面形状は、例えば、三角形形状などの多角形形状、楕円形状、Ｙ字形状などのアルファベット文字型形状、不定形形状、多葉形状、アスタリスク形状などの記号型形状、あるいはこれらの形状が複数結合した形状などであることができる。 The finer the average fiber diameter of the metal oxide fiber A, the thinner the thickness, and it is easy to provide a metal oxide fiber aggregate that meets the recent demands for lightness, thinness, and shortening. Therefore, the average fiber diameter is 10 μm or less. It is preferably present, more preferably 3 μm or less, and even more preferably 2 μm or less. On the other hand, if the average fiber diameter is too small, the mechanical strength of the metal oxide fiber aggregate may decrease, so 0.1 μm or more is appropriate. The "average fiber diameter" refers to the arithmetic average value of the fiber diameter at 50 points of the metal oxide fiber, and the "fiber diameter" is based on a 50-5000 times electron micrograph of a cross section of the metal oxide fiber. Refers to the diameter of the metal oxide fiber measured in. The metal oxide fiber A may have a deformed cross section in which the fiber cross section is not circular, and the method for measuring the fiber diameter of the metal oxide fiber A in the deformed cross section is to measure the cross section of the deformed cross section and have a circle having the cross section. The diameter of is regarded as the fiber diameter. The cross-sectional shape of the metal oxide fiber A having an irregular cross section is, for example, a polygonal shape such as a triangular shape, an alphabetic character shape such as an elliptical shape or a Y-shape, an irregular shape, a multi-leaf shape, or a symbol type such as an asterisk shape. It can be a shape, or a shape in which a plurality of these shapes are combined.
また、本発明の金属酸化物繊維Ａの平均繊維長は、特に限定するものではない。なお、本発明における「平均繊維長」は、５０本の金属酸化物繊維における各繊維長の算術平均値をいい、「繊維長」は、金属酸化物繊維を撮影した５０～５０００倍の電子顕微鏡写真を基に測定した、金属酸化物繊維の長軸方向における長さをいう。 Further, the average fiber length of the metal oxide fiber A of the present invention is not particularly limited. The "average fiber length" in the present invention refers to the arithmetic average value of each fiber length in 50 metal oxide fibers, and the "fiber length" is a 50 to 5000 times electron microscope in which the metal oxide fibers are photographed. The length in the long axis direction of the metal oxide fiber measured based on the photograph.
本発明の金属酸化物繊維集合体は、シリカを主体とする金属酸化物繊維Ａの他に、シリカ以外の金属酸化物を主体とする金属酸化物繊維Ｂを含む。金属酸化物繊維Ｂの主成分であるシリカ以外の金属酸化物としては、例えば、リチウム、ベリリウム、ホウ素、ナトリウム、マグネシウム、アルミニウム、リン、硫黄、カリウム、カルシウム、スカンジウム、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、ガリウム、ゲルマニウム、ヒ素、セレン、ルビジウム、ストロンチウム、イットリウム、ジルコニウム、ニオブ、モリブデン、カドミウム、インジウム、スズ、アンチモン、テルル、セシウム、バリウム、ランタン、ハフニウム、タンタル、タングステン、水銀、タリウム、鉛、ビスマス、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、又はルテチウムなどの金属酸化物が挙げられる。なお、シリカ以外の金属酸化物は金属を１種類のみ含んでいても、２種類以上含んでいてもよい。前記シリカ以外の金属酸化物が２種類以上の金属を含む場合、複合酸化物であっても、２種類以上の金属酸化物が複合せず混在した状態にあってもよい。これらの金属酸化物の中でも、金属酸化物繊維集合体を触媒用途に用いた時に有用である、酸化ランタン、酸化セリウム、アルミニウムの酸化物であるアルミナ、チタンの酸化物であるチタニア、ガドリニウムとセリウムの複合酸化物、リチウムとバナジウムの複合酸化物の少なくとも一つの金属酸化物であるのが好ましく、酸化ランタンと酸化セリウムの少なくとも一方を含んでいるのがより好ましい。 The metal oxide fiber aggregate of the present invention contains a metal oxide fiber B mainly composed of a metal oxide other than silica, in addition to the metal oxide fiber A mainly composed of silica. Examples of metal oxides other than silica, which is the main component of the metal oxide fiber B, include lithium, beryllium, boron, sodium, magnesium, aluminum, phosphorus, sulfur, potassium, calcium, scandium, titanium, vanadium, chromium, and manganese. , Iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, rubidium, strontium, ittrium, zirconium, niobium, molybdenum, cadmium, indium, tin, antimony, tellurium, cesium, barium, lantern, hafnium, tantalum , Tungsten, mercury, tarium, lead, bismuth, cerium, placeodim, neodym, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, turium, itterbium, or metal oxides such as lutetium. The metal oxide other than silica may contain only one type of metal or may contain two or more types of metal. When the metal oxide other than silica contains two or more kinds of metals, the composite oxide may be a composite oxide, or the two or more kinds of metal oxides may be in a mixed state without being composited. Among these metal oxides, lanthanum oxide, cerium oxide, alumina, which is an oxide of aluminum, titania, which is an oxide of titanium, gadrinium and cerium, which are useful when the metal oxide fiber aggregate is used as a catalyst. The composite oxide of the above, at least one metal oxide of the composite oxide of lithium and vanadium is preferable, and it is more preferable to contain at least one of lanthanum oxide and cerium oxide.
金属酸化物繊維Ｂに含まれるシリカ以外の金属酸化物の割合は、大きければ大きいほど、より金属酸化物繊維Ｂに含まれる金属酸化物による作用効果（触媒作用等）が効率よく得られることから、金属酸化物繊維Ｂに含まれるシリカ以外の金属酸化物の割合は、８０ｍａｓｓ％以上がより好ましく、９０ｍａｓｓ％以上が更に好ましく、１００ｍａｓｓ％が最も好ましい。なお、金属酸化物繊維Ｂには、シリカ以外の金属酸化物の他に、金属酸化物繊維Ａに含有することができる、染料などの有機成分や、ヒドロキシアパタイトやシリカ以外の金属酸化物などの無機成分を含有することができる。 The larger the proportion of the metal oxide other than silica contained in the metal oxide fiber B, the more efficiently the action and effect (catalytic action, etc.) of the metal oxide contained in the metal oxide fiber B can be obtained. The ratio of the metal oxide other than silica contained in the metal oxide fiber B is more preferably 80 mass% or more, further preferably 90 mass% or more, and most preferably 100 mass%. The metal oxide fiber B includes, in addition to metal oxides other than silica, organic components such as dyes that can be contained in the metal oxide fiber A, and metal oxides other than hydroxyapatite and silica. It can contain inorganic components.
金属酸化物繊維Ｂの平均繊維径は、細ければ細いほど、金属酸化物繊維Ｂの表面積が大きくなり、触媒などの用途に金属酸化物繊維集合体を用いる際に好ましいこと、また、厚さが薄く、近年の軽薄短小化の要望に合う金属酸化物繊維集合体を提供しやすいため、平均繊維径は１０μｍ以下であるのが好ましく、３μｍ以下であるのがより好ましく、２μｍ以下であるのが更に好ましい。一方、平均繊維径が細すぎると、金属酸化物繊維集合体の機械的強度が低下するおそれがあることから、０．０１μｍ以上が適当である。なお、金属酸化物繊維Ｂは金属酸化物繊維Ａと同様に繊維断面が円形でない異形断面であってもよい。また、本発明の金属酸化物繊維Ｂの平均繊維長は、特に限定するものではない。 The finer the average fiber diameter of the metal oxide fiber B, the larger the surface area of the metal oxide fiber B, which is preferable when the metal oxide fiber aggregate is used for applications such as catalysts, and the thickness. The average fiber diameter is preferably 10 μm or less, more preferably 3 μm or less, and more preferably 2 μm or less, because it is thin and it is easy to provide a metal oxide fiber aggregate that meets the recent demands for lightness, thinness, and shortening. Is more preferable. On the other hand, if the average fiber diameter is too small, the mechanical strength of the metal oxide fiber aggregate may decrease, so 0.01 μm or more is appropriate. As with the metal oxide fiber A, the metal oxide fiber B may have a deformed cross section in which the fiber cross section is not circular. Further, the average fiber length of the metal oxide fiber B of the present invention is not particularly limited.
本発明の金属酸化物繊維集合体における、シリカを主体とする金属酸化物繊維Ａ及びシリカ以外の金属酸化物繊維Ｂの合計量の割合は、より金属酸化物繊維集合体の強度が高くなるように、７０ｍａｓｓ％以上が好ましく、８０ｍａｓｓ％以上がより好ましく、９０ｍａｓｓ％以上が更に好ましい。なお、本発明の金属酸化物繊維集合体には、金属酸化物繊維Ａ及びＢの他に、例えば、金属酸化物繊維を接着する有機成分や無機成分を含んでいてもよい。 The ratio of the total amount of the metal oxide fiber A mainly composed of silica and the metal oxide fiber B other than silica in the metal oxide fiber aggregate of the present invention is such that the strength of the metal oxide fiber aggregate becomes higher. In addition, 70 mass% or more is preferable, 80 mass% or more is more preferable, and 90 mass% or more is further preferable. In addition to the metal oxide fibers A and B, the metal oxide fiber aggregate of the present invention may contain, for example, an organic component or an inorganic component for adhering the metal oxide fiber.
また、本発明の金属酸化物繊維Ａと金属酸化物繊維Ｂの合計量に対する金属酸化物繊維Ａの質量比は、金属酸化物繊維Ａの割合が低すぎると、金属酸化物繊維集合体の強度が低下するおそれがあることから、１０ｍａｓｓ％以上（１００ｍａｓｓ％を除く）が好ましく、２０ｍａｓｓ％以上（１００ｍａｓｓ％を除く）がより好ましく、３０ｍａｓｓ％以上（１００ｍａｓｓ％を除く）が更に好ましい。金属酸化物繊維集合体を触媒用途に用いる場合、金属酸化物繊維Ａと金属酸化物繊維Ｂの合計量に対する金属酸化物繊維Ａの質量比の上限については、金属酸化物繊維集合体を触媒に用いた際に金属酸化物繊維Ｂによる触媒活性が充分であるように、９９ｍａｓｓ％以下が好ましく、９５ｍａｓｓ％以下がより好ましく、９０ｍａｓｓ％以下が更に好ましい。 Further, the mass ratio of the metal oxide fiber A to the total amount of the metal oxide fiber A and the metal oxide fiber B of the present invention is such that if the ratio of the metal oxide fiber A is too low, the strength of the metal oxide fiber aggregate is obtained. 10 mass% or more (excluding 100 mass%) is preferable, 20 mass% or more (excluding 100 mass%) is more preferable, and 30 mass% or more (excluding 100 mass%) is further preferable. When the metal oxide fiber aggregate is used as a catalyst, the upper limit of the mass ratio of the metal oxide fiber A to the total amount of the metal oxide fiber A and the metal oxide fiber B is set by using the metal oxide fiber aggregate as a catalyst. 99 mass% or less is preferable, 95 mass% or less is more preferable, and 90 mass% or less is further preferable, so that the catalytic activity by the metal oxide fiber B is sufficient when used.
金属酸化物繊維集合体の形状は、特に限定するものではないが、例えば、直方体や立方体、円筒形や球状、シート状などであることができる。 The shape of the metal oxide fiber aggregate is not particularly limited, but may be, for example, a rectangular parallelepiped, a cube, a cylinder, a sphere, or a sheet.
次に、本発明の金属酸化物繊維集合体の製造方法の一例について説明する。 Next, an example of the method for producing the metal oxide fiber aggregate of the present invention will be described.
まず、（ｉ）ケイ素を含む物質を含む紡糸液ａと、ケイ素以外の金属を含む物質を含む紡糸液ｂを調製する工程、について説明する。 First, (i) a step of preparing a spinning liquid a containing a substance containing silicon and a spinning liquid b containing a substance containing a metal other than silicon will be described.
紡糸液ａは、後述の通り紡糸液ａからシリカを主体とする金属酸化物繊維Ａを紡糸することから、シリカ、またはケイ素塩やケイ素アルコキシドなどのケイ素を含む物質、溶媒または分散媒、必要に応じて粘度を調整するための高分子、あるいは、ケイ素塩を用いている場合はケイ素イオンと配位結合可能な高分子、及び触媒を準備する。 Since the spinning liquid a spins a metal oxide fiber A mainly composed of silica from the spinning liquid a as described later, it is necessary to use silica, a substance containing silicon such as a silicon salt or silicon alkoxide, a solvent or a dispersion medium. A polymer for adjusting the viscosity, or a polymer capable of coordinating with silicon ions when a silicon salt is used, and a catalyst are prepared accordingly.
ケイ素を含む物質のうち、ケイ素塩は、例えば、ケイ素を含むハロゲン化物、硝酸塩、硫酸塩、酢酸塩、シュウ酸塩等を１種類以上用いることができる。 Among the substances containing silicon, for example, one or more kinds of halides containing silicon, nitrates, sulfates, acetates, oxalates and the like can be used as the silicon salt.
また、溶媒または分散媒は特に限定するものではないが、例えば、アルコール類（例えば、メタノール、エタノール、プロパノールなど）、ジメチルホルムアミド、ジメチルアセトアミド、ケトン類（例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン、ジアセトンアルコールなど）、水などを挙げることができる。 The solvent or dispersion medium is not particularly limited, but for example, alcohols (eg, methanol, ethanol, propanol, etc.), dimethylformamide, dimethylacetamide, ketones (eg, acetone, methylethylketone, methylisobutylketone, diisobutyl). Ketone, cyclohexanone, diacetone alcohol, etc.), water, etc. can be mentioned.
更に、粘度を調整するための高分子についても特に限定するものではなく、例えば、ポリビニルアルコール、ポリビニルピロリドンなどが挙げられる。 Further, the polymer for adjusting the viscosity is not particularly limited, and examples thereof include polyvinyl alcohol and polyvinylpyrrolidone.
更に、ケイ素イオンと配位結合可能な高分子についても特に限定するものではないが、例えば、ポリビニルアルコール、ポリビニルピロリドン、無水マレイン酸系ポリマー、カルボン酸系ポリマー、アミノアルコール系ポリマー、ポルフィリンアレイ、チオシアン酸系ポリマー、エチレンジアミン系ポリマーなどが挙げられる。 Further, the polymer capable of coordinating with silicon ions is not particularly limited, and for example, polyvinyl alcohol, polyvinylpyrrolidone, maleic anhydride-based polymer, carboxylic acid-based polymer, amino alcohol-based polymer, porphyrin array, and thiocyan. Examples thereof include acid-based polymers and ethylenediamine-based polymers.
紡糸液ａの粘度は、紡糸後焼成してシリカを主体とする金属酸化物繊維Ａを形成することができれば特に限定するものではないが、１００～１００００ｍＰａ・ｓであることができる。 The viscosity of the spinning liquid a is not particularly limited as long as it can form the metal oxide fiber A mainly composed of silica by firing after spinning, but it can be 100 to 10,000 mPa · s.
また、紡糸液ｂは、後述の通り紡糸液ｂからシリカ以外の金属酸化物を主体とする金属酸化物繊維Ｂを紡糸することから、上述のシリカ以外の金属酸化物、あるいはケイ素以外の塩や金属アルコキシドなどの金属を含む物質、溶媒または分散媒、必要に応じて粘度を調整するための、あるいは、金属塩を用いている場合は金属イオンと配位結合可能な高分子、及び触媒を準備する。ケイ素以外の塩は、ケイ素塩と同様に、例えば、ハロゲン化物、硝酸塩、硫酸塩、酢酸塩、シュウ酸塩等を１種類以上用いることができる。また、紡糸液ｂに用いる溶媒または分散媒は、紡糸液ａの溶媒または分散媒と同様の物を用いることができる。更に、粘度を調整するための高分子、金属イオンと配位結合可能な高分子についても、紡糸液ａと同様の物を用いることができる。 Further, since the spinning liquid b spins the metal oxide fiber B mainly composed of a metal oxide other than silica from the spinning liquid b as described later, the above-mentioned metal oxide other than silica or a salt other than silicon can be used. Prepare a metal-containing substance such as a metal alkoxide, a solvent or dispersion medium, a polymer for adjusting the viscosity if necessary, or a polymer that can coordinate with metal ions when using a metal salt, and a catalyst. do. As the salt other than silicon, for example, one or more kinds of halides, nitrates, sulfates, acetates, oxalates and the like can be used in the same manner as the silicon salt. Further, as the solvent or dispersion medium used for the spinning liquid b, the same solvent or dispersion medium as that of the spinning liquid a can be used. Further, as a polymer for adjusting the viscosity and a polymer capable of coordinating and bonding with metal ions, the same one as the spinning solution a can be used.
紡糸液ｂの粘度は、紡糸液ｂに含まれる金属によって適した粘度が異なることから、特に限定するものではない。 The viscosity of the spinning liquid b is not particularly limited because the suitable viscosity differs depending on the metal contained in the spinning liquid b.
次に、（ｉｉ）紡糸液ａを紡糸し焼成することで、シリカを主体とする金属酸化物繊維Ａを調製する工程、について説明する。紡糸液ａの紡糸方法は、紡糸後焼成してシリカを主体とする金属酸化物繊維Ａを形成することができる限り、特に限定するものではないが、例えば、常法の乾式紡糸法、静電紡糸法、特開２００５－２６４３７４号公報に開示されているような、静電紡糸の際に繊維とは反対極性のイオンを照射する紡糸方法、特開２００９－２８７１３８号公報に開示されているような、ガスの剪断作用により紡糸する方法、或いは特開２０１２－１５４００９号公報に開示されているような、電界の作用に加えてガスの剪断力を作用させて紡糸する方法、を挙げることができる。これらの中でも、静電紡糸法によれば、繊維径が小さく、比表面積の大きい金属酸化物繊維を紡糸することができるため好適である。なお、紡糸液の導電率が高いなど、静電紡糸法により安定して紡糸できない場合には、電界の作用に加えてガスの剪断作用を併用することにより、又は、ガスの剪断作用により紡糸する方法によれば、安定して紡糸することができる。 Next, (ii) a step of preparing the metal oxide fiber A mainly composed of silica by spinning and firing the spinning liquid a will be described. The spinning method of the spinning liquid a is not particularly limited as long as it can form the metal oxide fiber A mainly composed of silica by firing after spinning, but for example, a conventional dry spinning method or electrostatic. Spinning method, a spinning method for irradiating ions having a polarity opposite to that of a fiber during electrostatic spinning, as disclosed in JP-A-2005-264374, as disclosed in JP-A-2009-287138. Examples thereof include a method of spinning by a gas shearing action, and a method of spinning by applying a gas shearing force in addition to the action of an electric field as disclosed in Japanese Patent Application Laid-Open No. 2012-15409. .. Among these, the electrostatic spinning method is suitable because it can spin metal oxide fibers having a small fiber diameter and a large specific surface area. If the spinning solution cannot be stably spun by the electrostatic spinning method due to high conductivity, the spinning is performed by using the gas shearing action in addition to the electric field action, or by the gas shearing action. According to the method, the spinning can be performed stably.
また、紡糸液ａを紡糸した後、紡糸液に含まれる金属成分の酸化や、紡糸液に含まれるポリマーの除去を目的とした焼成を行う。なお、焼成は、例えば、オーブン、焼結炉などの装置を用いて実施することができ、その温度は、１００～１５００℃が好ましく、２００～１２００℃がより好ましく、４００～１０００℃が更に好ましい。また、焼成時間は１時間以上が好ましい。 Further, after the spinning liquid a is spun, firing is performed for the purpose of oxidizing the metal component contained in the spinning liquid and removing the polymer contained in the spinning liquid. The firing can be carried out using, for example, an apparatus such as an oven or a sintering furnace, and the temperature thereof is preferably 100 to 1500 ° C, more preferably 200 to 1200 ° C, still more preferably 400 to 1000 ° C. .. The firing time is preferably 1 hour or more.
次に、（ｉｉｉ）紡糸液ｂを紡糸し焼成することで、シリカ以外の金属酸化物を主体とする金属酸化物繊維Ｂを調製する工程、について説明する。紡糸液ｂの紡糸方法は、紡糸液ａの紡糸方法と同様の方法を採用することができる。また、焼成に用いる装置も紡糸液ａと同様の装置を採用することができる。焼成温度及び焼成時間については、紡糸液ｂに含まれる金属によって適した焼成温度及び焼成時間が異なるため、特に限定するものではない。 Next, (iii) a step of preparing a metal oxide fiber B mainly composed of a metal oxide other than silica by spinning and firing the spinning liquid b will be described. As the spinning method of the spinning liquid b, the same method as the spinning method of the spinning liquid a can be adopted. Further, as the apparatus used for firing, the same apparatus as the spinning liquid a can be adopted. The firing temperature and firing time are not particularly limited because the suitable firing temperature and firing time differ depending on the metal contained in the spinning liquid b.
次に、（ｉｖ）金属酸化物繊維Ａと金属酸化物繊維Ｂを混合し、金属酸化物繊維集合体を調製する工程、について説明する。 Next, (iv) a step of mixing the metal oxide fiber A and the metal oxide fiber B to prepare a metal oxide fiber aggregate will be described.
金属酸化物繊維Ａと金属酸化物繊維Ｂを混合する方法としては、特に限定するものではないが、例えば、金属酸化物繊維Ａ及びＢを、液体分散媒に分散させ、濾過することで混合する方法（分散媒は、前述の紡糸液に用いることができると例示したような溶媒又は分散媒を用いることができる）や、金属酸化物繊維Ａ及びＢを粉砕し混ぜ合わせるなど、気体中で混合する方法が挙げられる。なお、効率よく金属酸化物繊維Ａと金属酸化物繊維Ｂを混合して金属酸化物繊維集合体を調製するため、混合する前に金属酸化物繊維ＡあるいはＢを乳鉢やプレス機など公知の方法で粉砕し、繊維長を短くしてもよい。また、金属酸化物繊維集合体の強度向上のため、金属酸化物繊維Ａと金属酸化物繊維Ｂを混合する際、または、混合した後に金属酸化物繊維Ａ、Ｂを接着する有機成分や無機成分を付与し、金属酸化物繊維集合体を調製してもよい。 The method for mixing the metal oxide fiber A and the metal oxide fiber B is not particularly limited, but for example, the metal oxide fibers A and B are dispersed in a liquid dispersion medium and mixed by filtering. The method (the dispersion medium can be a solvent or a dispersion medium as exemplified as that it can be used for the above-mentioned spinning solution) or the metal oxide fibers A and B are crushed and mixed in a gas. There is a way to do it. In order to efficiently mix the metal oxide fiber A and the metal oxide fiber B to prepare the metal oxide fiber aggregate, a known method such as a dairy pot or a press machine is used to mix the metal oxide fiber A or B before mixing. May be crushed with to shorten the fiber length. Further, in order to improve the strength of the metal oxide fiber aggregate, an organic component or an inorganic component that adheres the metal oxide fibers A and B when or after the metal oxide fiber A and the metal oxide fiber B are mixed. May be applied to prepare a metal oxide fiber aggregate.
本発明の金属酸化物繊維集合体は、形崩れを起こしにくく取り扱い性に優れるため、触媒や、熱伝導性部材など様々な用途に用いることができる。特に、金属酸化物繊維集合体に酸化ランタン、酸化セリウム、アルミニウムの酸化物であるアルミナ、チタンの酸化物であるチタニア、ガドリニウムとセリウムの複合酸化物、リチウムとバナジウムの複合酸化物といった触媒作用を示す金属酸化物が含まれている場合、触媒用途に好適に用いることができる。 Since the metal oxide fiber aggregate of the present invention does not easily lose its shape and is excellent in handleability, it can be used for various purposes such as a catalyst and a heat conductive member. In particular, the metal oxide fiber aggregate has catalytic action such as lanthanum oxide, cerium oxide, alumina which is an oxide of aluminum, titania which is an oxide of titanium, a composite oxide of gadrinium and cerium, and a composite oxide of lithium and vanadium. When the indicated metal oxide is contained, it can be suitably used for catalytic applications.
以下に、本発明の実施例を記載するが、本発明は以下の実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to the following examples.
（実施例１）
（金属酸化物繊維Ａの調製）
まず、テトラエトキシシラン、エタノール、水、１ｍｏｌ／Ｌの塩酸を１：５：２：０．００３のモル比で混合し、温度８０℃で１５時間の還流操作を行い、次いで、溶媒をロータリーエバポレーターにより除去して濃縮した後、温度８０℃に加熱して、粘度が１０００ｍＰａ・ｓのゾル溶液である紡糸液ａを調製した。次に、得られた紡糸液ａを、特開２００５－２６４３７４号公報に開示されているような、静電紡糸の際に繊維とは反対極性のイオンを照射する紡糸方法により紡糸しコンベアに集積させ、金属酸化物繊維Ａ前駆体を形成した。
なお、前記紡糸方法は、特開２００５－２６４３７４号公報の実施例８と同じ紡糸条件で実施した。詳細を以下に示す。
紡糸液ａの吐出量：０．５ｇ／時間
紡糸ノズル：内径０．４ｍｍの金属製注射針（先端カット）
紡糸ノズルと対向電極との距離：２０ｃｍ
対向電極及びイオン発生電極（両電極を兼ねる）：ステンレス板（誘起電極）上に厚さ１ｍｍのアルミナ膜（誘電体基板）を溶射し、その上に直径３０μｍのタングステンワイヤ（放電電極）を１０ｍｍの等間隔で張った沿面放電素子（タングステンワイヤ面を紡糸ノズルと対向させると共に接地し、ステンレス板とタングステンワイヤ間に交流高電圧電源により５０Ｈｚの交流高電圧を印加）
第１高電圧電源：＋１０ｋＶ
第２高電圧電源：±５ｋＶ（交流沿面のピーク電圧：５ｋＶ、５０Ｈｚ）
紡糸室内の雰囲気：温度２５℃、湿度４０％ＲＨ
次に、得られた金属酸化物繊維Ａ前駆体を空気雰囲気下、温度８００℃で２時間焼成して熱処理し、プレス機で粉砕（５ＭＰａ、１０秒間）し、シリカから構成された金属酸化物繊維Ａ（平均繊維径：１μｍ、平均繊維長：２００μｍ）を得た。
(Example 1)
(Preparation of metal oxide fiber A)
First, tetraethoxysilane, ethanol, water, and 1 mol / L hydrochloric acid are mixed at a molar ratio of 1: 5: 2: 0.003, and a reflux operation is performed at a temperature of 80 ° C. for 15 hours, and then the solvent is used as a rotary evaporator. After removing and concentrating the mixture, the mixture was heated to a temperature of 80 ° C. to prepare a spinning solution a which is a sol solution having a viscosity of 1000 mPa · s. Next, the obtained spinning liquid a is spun by a spinning method of irradiating ions having a polarity opposite to that of the fiber during electrostatic spinning as disclosed in Japanese Patent Application Laid-Open No. 2005-264374, and accumulated in a conveyor. The metal oxide fiber A precursor was formed.
The spinning method was carried out under the same spinning conditions as in Example 8 of JP-A-2005-264374. Details are shown below.
Discharge amount of spinning liquid a: 0.5 g / hour Spinning nozzle: Metal injection needle with inner diameter 0.4 mm (tip cut)
Distance between spinning nozzle and counter electrode: 20 cm
Opposite electrode and ion generating electrode (also serving as both electrodes): A 1 mm thick alumina film (dielectric substrate) is sprayed onto a stainless steel plate (induced electrode), and a tungsten wire (discharge electrode) with a diameter of 30 μm is placed on it by 10 mm. Creeping discharge element stretched at equal intervals (Tungsten wire surface faces the spinning nozzle and is grounded, and 50Hz AC high voltage is applied between the stainless plate and the tungsten wire by AC high voltage power supply)
1st high voltage power supply: + 10kV
Second high voltage power supply: ± 5 kV (peak voltage along the AC surface: 5 kV, 50 Hz)
Atmosphere in the spinning room: temperature 25 ° C, humidity 40% RH
Next, the obtained metal oxide fiber A precursor was calcined in an air atmosphere at a temperature of 800 ° C. for 2 hours to be heat-treated, and pulverized with a press machine (5 MPa, 10 seconds) to obtain a metal oxide composed of silica. Fiber A (average fiber diameter: 1 μm, average fiber length: 200 μm) was obtained.
（金属酸化物繊維Ｂの調製）
硝酸ランタン六水和物（６．９ｍｍｏｌ）、硝酸セリウム六水和物（０．４６ｍｍｏｌ）、及びアセト酢酸エチル（７．３６ｍｍｏｌ）をエタノール（１００ｍｍｏｌ）に加えて１時間撹拌を行い、金属塩を溶解させて、溶液を得た。次いで、前記溶液１．６７ｇ、無水マレイン酸ポリマー１．５ｇ、Ｎ，Ｎ－ジメチルホルムアミド６．８３ｇとなるように混合して、紡糸液ｂ１を調製した。
次に、得られた紡糸液ｂ１を、ガスのせん断作用と電界の作用によって紡糸する方法により紡糸して、集積させ、金属酸化物繊維Ｂ１前駆体を形成した。
なお、ガスのせん断作用と電界の作用によって紡糸する方法は、特開２０１２－１５４００９号公報の実施例１と同じ紡糸条件で実施した。詳細を以下に示す。
紡糸液ｂ１の吐出量：１．５ｇ／時間
ガス吐出ノズルからの空気吐出圧力：０．５ＭＰａ
ガス吐出ノズルからの吐出空気温度：２５℃
液吐出ノズル（紡糸ノズル）への印加電圧：１０ｋＶ
紡糸室内の雰囲気：温度２５℃、湿度４０％ＲＨ
次に、得られた金属酸化物繊維Ｂ１前駆体を空気雰囲気下、温度８００℃で２時間焼成して熱処理し、酸化ランタンと酸化セリウムが混在し、前記２種類の金属酸化物から構成された金属酸化物繊維Ｂ１（平均繊維径：１００ｎｍ、平均繊維長：３０μｍ）を得た。
(Preparation of metal oxide fiber B)
Lanthanum nitrate hexahydrate (6.9 mmol), cerium nitrate hexahydrate (0.46 mmol), and ethyl acetoacetate (7.36 mmol) were added to ethanol (100 mmol), and the mixture was stirred for 1 hour to remove a metal salt. It was dissolved to obtain a solution. Then, 1.67 g of the solution, 1.5 g of maleic anhydride polymer, and 6.83 g of N, N-dimethylformamide were mixed to prepare a spinning solution b1.
Next, the obtained spinning liquid b1 was spun by a method of spinning by the action of a gas shearing action and an electric field and accumulated to form a metal oxide fiber B1 precursor.
The method of spinning by the action of the shearing action of the gas and the action of the electric field was carried out under the same spinning conditions as in Example 1 of JP2012-15409A. Details are shown below.
Discharge amount of spinning liquid b1: 1.5 g / hour Air discharge pressure from gas discharge nozzle: 0.5 MPa
Discharge air temperature from gas discharge nozzle: 25 ° C
Voltage applied to the liquid discharge nozzle (spinning nozzle): 10 kV
Atmosphere in the spinning room: temperature 25 ° C, humidity 40% RH
Next, the obtained metal oxide fiber B1 precursor was heat-treated by firing at a temperature of 800 ° C. for 2 hours in an air atmosphere, and lanthanum oxide and cerium oxide were mixed and composed of the above two types of metal oxides. Metal oxide fiber B1 (average fiber diameter: 100 nm, average fiber length: 30 μm) was obtained.
（金属酸化物繊維集合体の調製）
まず、テトラエトキシシラン、エタノール、水、１ｍｏｌ／Ｌの硝酸を１：７．２：１１：０．０００３のモル比で混合し、２５℃で１５時間攪拌を行ったゾル溶液を用意し、シリカ固形分が０．１％となるようにエタノールを加えた、シリカ系バインダを調製した。
次に、金属酸化物繊維Ａと金属酸化物繊維Ｂ１を質量比９９：１でエタノールに混合し分散させ、金属酸化物繊維Ａ及びＢ１が分散された分散液を桐山ロートで吸引濾過し、円筒形の金属酸化物繊維集合体前駆体を調製した。
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度８００℃で２時間焼成して熱処理し、円筒形の金属酸化物繊維集合体を得た。この金属酸化物繊維集合体は、円筒形の形状を保っており、金属酸化物繊維集合体をピンセットで持ち上げたときに、金属酸化物繊維集合体が形崩れを起こさなかった。
(Preparation of metal oxide fiber aggregate)
First, a sol solution was prepared by mixing tetraethoxysilane, ethanol, water and 1 mol / L nitric acid at a molar ratio of 1: 7.2: 11: 0.0003 and stirring at 25 ° C. for 15 hours to prepare silica. A silica-based binder was prepared by adding ethanol so that the solid content was 0.1%.
Next, the metal oxide fiber A and the metal oxide fiber B1 are mixed and dispersed in ethanol at a mass ratio of 99: 1, and the dispersion liquid in which the metal oxide fibers A and B1 are dispersed is suction-filtered by a Kiriyama funnel and cylindrical. A metal oxide fiber aggregate precursor in the form was prepared.
Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was fired at a temperature of 800 ° C. for 2 hours in an air atmosphere to heat-treat it into a cylindrical shape. The metal oxide fiber aggregate of the above was obtained. The metal oxide fiber aggregate maintained a cylindrical shape, and when the metal oxide fiber aggregate was lifted with tweezers, the metal oxide fiber aggregate did not lose its shape.
（実施例２）
金属酸化物繊維Ａと金属酸化物繊維Ｂ１を質量比３０：７０でエタノールに混合し分散させ、金属酸化物繊維Ａ及びＢ１が分散された分散液を桐山ロートで吸引濾過して円筒形の金属酸化物繊維集合体前駆体を調製したことを除いては、実施例１と同様にして、円筒形の金属酸化物繊維集合体を調製した。この金属酸化物繊維集合体は、円筒形の形状を保っており、金属酸化物繊維集合体をピンセットで持ち上げたときに、金属酸化物繊維集合体が形崩れを起こさなかった。
(Example 2)
The metal oxide fiber A and the metal oxide fiber B1 are mixed and dispersed in ethanol at a mass ratio of 30:70, and the dispersion liquid in which the metal oxide fibers A and B1 are dispersed is suction-filtered by a Kiriyama funnel to form a cylindrical metal. A cylindrical metal oxide fiber aggregate was prepared in the same manner as in Example 1 except that the oxide fiber aggregate precursor was prepared. The metal oxide fiber aggregate maintained a cylindrical shape, and when the metal oxide fiber aggregate was lifted with tweezers, the metal oxide fiber aggregate did not lose its shape.
（実施例３）
金属酸化物繊維Ａと金属酸化物繊維Ｂ１を質量比２０：８０でエタノールに混合し分散させ、金属酸化物繊維Ａ及びＢ１が分散された分散液を桐山ロートで吸引濾過して円筒形の金属酸化物繊維集合体前駆体を調製したことを除いては、実施例１と同様にして、円筒形の金属酸化物繊維集合体を調製した。この金属酸化物繊維集合体は、円筒形の形状を保っており、金属酸化物繊維集合体をピンセットで持ち上げたときに、金属酸化物繊維集合体が形崩れを起こさなかった。
(Example 3)
The metal oxide fiber A and the metal oxide fiber B1 are mixed and dispersed in ethanol at a mass ratio of 20:80, and the dispersion liquid in which the metal oxide fibers A and B1 are dispersed is suction-filtered by a Kiriyama funnel to form a cylindrical metal. A cylindrical metal oxide fiber aggregate was prepared in the same manner as in Example 1 except that the oxide fiber aggregate precursor was prepared. The metal oxide fiber aggregate maintained a cylindrical shape, and when the metal oxide fiber aggregate was lifted with tweezers, the metal oxide fiber aggregate did not lose its shape.
（実施例４）
金属酸化物繊維Ａと金属酸化物繊維Ｂ１を質量比１０：９０でエタノールに混合し分散させ、金属酸化物繊維Ａ及びＢ１が分散された分散液を桐山ロートで吸引濾過して円筒形の金属酸化物繊維集合体前駆体を調製したことを除いては、実施例１と同様にして、円筒形の金属酸化物繊維集合体を調製した。この金属酸化物繊維集合体は、円筒形の形状を保っており、金属酸化物繊維集合体をピンセットで持ち上げたときに、金属酸化物繊維集合体が形崩れを起こさなかった。
(Example 4)
The metal oxide fiber A and the metal oxide fiber B1 are mixed and dispersed in ethanol at a mass ratio of 10:90, and the dispersion liquid in which the metal oxide fibers A and B1 are dispersed is suction-filtered by a Kiriyama funnel to form a cylindrical metal. A cylindrical metal oxide fiber aggregate was prepared in the same manner as in Example 1 except that the oxide fiber aggregate precursor was prepared. The metal oxide fiber aggregate maintained a cylindrical shape, and when the metal oxide fiber aggregate was lifted with tweezers, the metal oxide fiber aggregate did not lose its shape.
（実施例５）
（金属酸化物繊維Ａの調製）
実施例１と同様の方法で、金属酸化物繊維Ａを調製した。
(Example 5)
(Preparation of metal oxide fiber A)
The metal oxide fiber A was prepared in the same manner as in Example 1.
（金属酸化物繊維Ｂの調製）
硝酸ランタン六水和物（６．５４ｍｍｏｌ）、硝酸セリウム六水和物（０．８１ｍｍｏｌ）、及びアセト酢酸エチル（７．３６ｍｍｏｌ）をエタノール（１００ｍｍｏｌ）に加えて１時間撹拌を行い、金属塩を溶解させて、溶液を得た。次いで、前記溶液１．６７ｇ、無水マレイン酸ポリマー１．５ｇ、Ｎ，Ｎ－ジメチルホルムアミド６．８３ｇとなるように混合して、紡糸液ｂ２を調製した。
次に、得られた紡糸液ｂ２を、ガスのせん断作用と電界の作用によって紡糸する方法により紡糸して、集積させ、金属酸化物繊維Ｂ２前駆体を形成した。
なお、ガスのせん断作用と電界の作用によって紡糸する方法は、特開２０１２－１５４００９号公報の実施例１と同じ紡糸条件で実施した。詳細を以下に示す。
紡糸液ｂ２の吐出量：１．５ｇ／時間
ガス吐出ノズルからの空気吐出圧力：０．５ＭＰａ
ガス吐出ノズルからの吐出空気温度：２５℃
液吐出ノズル（紡糸ノズル）への印加電圧：１０ｋＶ
紡糸室内の雰囲気：温度２５℃、湿度４０％ＲＨ
次に、得られた金属酸化物繊維Ｂ２前駆体を空気雰囲気下、温度８００℃で２時間焼成して熱処理し、酸化ランタンと酸化セリウムが混在し、前記２種類の金属酸化物から構成された金属酸化物繊維Ｂ２（平均繊維径：１００ｎｍ、平均繊維長：３０μｍ）を得た。
(Preparation of metal oxide fiber B)
Lanthanum nitrate hexahydrate (6.54 mmol), cerium nitrate hexahydrate (0.81 mmol), and ethyl acetoacetate (7.36 mmol) were added to ethanol (100 mmol), and the mixture was stirred for 1 hour to remove a metal salt. It was dissolved to obtain a solution. Then, 1.67 g of the solution, 1.5 g of maleic anhydride polymer, and 6.83 g of N, N-dimethylformamide were mixed to prepare a spinning solution b2.
Next, the obtained spinning liquid b2 was spun by a method of spinning by the shearing action of gas and the action of an electric field and accumulated to form a metal oxide fiber B2 precursor.
The method of spinning by the action of the shearing action of the gas and the action of the electric field was carried out under the same spinning conditions as in Example 1 of JP2012-15409A. Details are shown below.
Discharge amount of spinning liquid b2: 1.5 g / hour Air discharge pressure from gas discharge nozzle: 0.5 MPa
Discharge air temperature from gas discharge nozzle: 25 ° C
Voltage applied to the liquid discharge nozzle (spinning nozzle): 10 kV
Atmosphere in the spinning room: temperature 25 ° C, humidity 40% RH
Next, the obtained metal oxide fiber B2 precursor was heat-treated by firing at a temperature of 800 ° C. for 2 hours in an air atmosphere, and lanthanum oxide and cerium oxide were mixed and composed of the above two types of metal oxides. Metal oxide fiber B2 (average fiber diameter: 100 nm, average fiber length: 30 μm) was obtained.
（金属酸化物繊維集合体の調製）
まず、実施例１と同じシリカ系バインダを調製した。次に、金属酸化物繊維Ａと金属酸化物繊維Ｂ２を質量比９９：１でエタノールに混合し分散させ、金属酸化物繊維Ａ及びＢ２が分散された分散液を桐山ロートで吸引濾過し、金属酸化物繊維集合体前駆体を調製した。
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度８００℃で２時間焼成して熱処理し、円筒形の金属酸化物繊維集合体を得た。この金属酸化物繊維集合体は、形崩れを起こさず成型性を有するものであった。
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度８００℃で２時間焼成して熱処理し、円筒形の金属酸化物繊維集合体を得た。この金属酸化物繊維集合体は、円筒形の形状を保っており、金属酸化物繊維集合体をピンセットで持ち上げたときに、金属酸化物繊維集合体が形崩れを起こさなかった。
(Preparation of metal oxide fiber aggregate)
First, the same silica-based binder as in Example 1 was prepared. Next, the metal oxide fiber A and the metal oxide fiber B2 are mixed and dispersed in ethanol at a mass ratio of 99: 1, and the dispersion liquid in which the metal oxide fibers A and B2 are dispersed is suction-filtered by a Kiriyama funnel to metal. Oxide fiber aggregate precursors were prepared.
Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was fired at a temperature of 800 ° C. for 2 hours in an air atmosphere to heat-treat it into a cylindrical shape. The metal oxide fiber aggregate of the above was obtained. This metal oxide fiber aggregate did not lose its shape and had moldability.
Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was fired at a temperature of 800 ° C. for 2 hours in an air atmosphere to heat-treat it into a cylindrical shape. The metal oxide fiber aggregate of the above was obtained. The metal oxide fiber aggregate maintained a cylindrical shape, and when the metal oxide fiber aggregate was lifted with tweezers, the metal oxide fiber aggregate did not lose its shape.
（実施例６）
（金属酸化物繊維Ａの調製）
実施例１と同様の方法で、金属酸化物繊維Ａを調製した。
(Example 6)
(Preparation of metal oxide fiber A)
The metal oxide fiber A was prepared in the same manner as in Example 1.
（金属酸化物繊維Ｂの調製）
硝酸ランタン六水和物（３．６８ｍｍｏｌ）、硝酸セリウム六水和物（３．６８ｍｍｏｌ）、及びアセト酢酸エチル（７．３６ｍｍｏｌ）をエタノール（１００ｍｍｏｌ）に加えて１時間撹拌を行い、金属塩を溶解させて、溶液を得た。次いで、前記溶液１．６７ｇ、無水マレイン酸ポリマー１．５ｇ、Ｎ，Ｎ－ジメチルホルムアミド６．８３ｇとなるように混合して、紡糸液ｂ３を調製した。
次に、得られた紡糸液ｂ３を、ガスのせん断作用と電界の作用によって紡糸する方法により紡糸して、集積させ、金属酸化物繊維Ｂ３前駆体を形成した。なお、ガスのせん断作用と電界の作用によって紡糸する方法は、特開２０１２－１５４００９号公報の実施例１と同じ紡糸条件で実施した。詳細を以下に示す。
紡糸液ｂ３の吐出量：１．５ｇ／時間
ガス吐出ノズルからの空気吐出圧力：０．５ＭＰａ
ガス吐出ノズルからの吐出空気温度：２５℃
液吐出ノズル（紡糸ノズル）への印加電圧：１０ｋＶ
紡糸室内の雰囲気：温度２５℃、湿度４０％ＲＨ
次に、得られた金属酸化物繊維Ｂ３前駆体を空気雰囲気下、温度８００℃で２時間焼成して熱処理し、酸化ランタンと酸化セリウムが混在し、前記２種類の金属酸化物から構成された金属酸化物繊維Ｂ３（平均繊維径：１００ｎｍ、平均繊維長：３０μｍ）を得た。
(Preparation of metal oxide fiber B)
Lanthanum nitrate hexahydrate (3.68 mmol), cerium nitrate hexahydrate (3.68 mmol), and ethyl acetoacetate (7.36 mmol) were added to ethanol (100 mmol), and the mixture was stirred for 1 hour to remove a metal salt. It was dissolved to obtain a solution. Then, 1.67 g of the solution, 1.5 g of maleic anhydride polymer, and 6.83 g of N, N-dimethylformamide were mixed to prepare a spinning solution b3.
Next, the obtained spinning liquid b3 was spun by a method of spinning by the action of a gas shearing action and an electric field and accumulated to form a metal oxide fiber B3 precursor. The method of spinning by the action of the shearing action of the gas and the action of the electric field was carried out under the same spinning conditions as in Example 1 of JP2012-15409A. Details are shown below.
Discharge amount of spinning liquid b3: 1.5 g / hour Air discharge pressure from gas discharge nozzle: 0.5 MPa
Discharge air temperature from gas discharge nozzle: 25 ° C
Voltage applied to the liquid discharge nozzle (spinning nozzle): 10 kV
Atmosphere in the spinning room: temperature 25 ° C, humidity 40% RH
Next, the obtained metal oxide fiber B3 precursor was heat-treated by firing at a temperature of 800 ° C. for 2 hours in an air atmosphere, and lanthanum oxide and cerium oxide were mixed and composed of the above two types of metal oxides. Metal oxide fiber B3 (average fiber diameter: 100 nm, average fiber length: 30 μm) was obtained.
（金属酸化物繊維集合体の調製）
まず、実施例１と同じシリカ系バインダを調製した。次に、金属酸化物繊維Ａと金属酸化物繊維Ｂ３を質量比９９：１でエタノールに混合し分散させ、金属酸化物繊維Ａ及びＢ３が分散された分散液を桐山ロートで吸引濾過し、円筒形の金属酸化物繊維集合体前駆体を調製した。
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度８００℃で２時間焼成して熱処理し、円筒形の金属酸化物繊維集合体を得た。この金属酸化物繊維集合体は、円筒形の形状を保っており、金属酸化物繊維集合体をピンセットで持ち上げたときに、金属酸化物繊維集合体が形崩れを起こさなかった。
(Preparation of metal oxide fiber aggregate)
First, the same silica-based binder as in Example 1 was prepared. Next, the metal oxide fiber A and the metal oxide fiber B3 are mixed and dispersed in ethanol at a mass ratio of 99: 1, and the dispersion liquid in which the metal oxide fibers A and B3 are dispersed is suction-filtered by a Kiriyama funnel to form a cylinder. A metal oxide fiber aggregate precursor in the form was prepared.
Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was fired at a temperature of 800 ° C. for 2 hours in an air atmosphere to heat-treat it into a cylindrical shape. The metal oxide fiber aggregate of the above was obtained. The metal oxide fiber aggregate maintained a cylindrical shape, and when the metal oxide fiber aggregate was lifted with tweezers, the metal oxide fiber aggregate did not lose its shape.
（実施例７）
（金属酸化物繊維Ａの調製）
実施例１と同様の方法で、金属酸化物繊維Ａを調製した。
(Example 7)
(Preparation of metal oxide fiber A)
The metal oxide fiber A was prepared in the same manner as in Example 1.
（金属酸化物繊維Ｂの調製）
まず、アルミニウムｓｅｃ－ブトキシド、乳酸エチル、テトラブチルアンモニウムヒドロキシド、水、２－プロパノールを１：５：０．００２５：１：５のモル比で混合し、温度７０℃で１５時間加熱撹拌し、縮重合させた。そして、エバポレータにより濃縮した後、粘度が２０００～３０００ｍＰａ・ｓになるまで増粘させて、紡糸液ｂ４を得た。
次に、得られた紡糸液ｂ４を、静電紡糸法により紡糸するとともに、アースされたドラムに繊維を集積させ、金属酸化物繊維Ｂ４前駆体を形成した。詳細を以下に示す。
紡糸液ｂ４の吐出量：０．５ｇ／時間
ノズル先端とドラム捕集体との距離：１０ｃｍ
紡糸容器内の温湿度：２５℃、３０％ＲＨ
ノズルへの印加電圧：＋１０ｋＶ
次に、得られた金属酸化物繊維Ｂ４前駆体を空気雰囲気下、温度１２００℃で２時間焼成して熱処理し、プレス機で粉砕（２０ＭＰａ、３秒間）し、アルミナから構成された金属酸化物繊維Ｂ４（平均繊維径：０．７μｍ、平均繊維長：５０μｍ）を得た。
(Preparation of metal oxide fiber B)
First, aluminum sec-butoxide, ethyl lactate, tetrabutylammonium hydroxide, water, and 2-propanol were mixed at a molar ratio of 1: 5: 0.0025: 1: 5, heated and stirred at a temperature of 70 ° C. for 15 hours. It was polycondensed. Then, after concentrating with an evaporator, the viscosity was increased to 2000 to 3000 mPa · s to obtain a spinning liquid b4.
Next, the obtained spinning liquid b4 was spun by an electrostatic spinning method, and the fibers were accumulated on a grounded drum to form a metal oxide fiber B4 precursor. Details are shown below.
Discharge amount of spinning liquid b4: 0.5 g / hour Distance between nozzle tip and drum collector: 10 cm
Temperature and humidity in the spinning container: 25 ° C, 30% RH
Voltage applied to the nozzle: + 10kV
Next, the obtained metal oxide fiber B4 precursor was calcined in an air atmosphere at a temperature of 1200 ° C. for 2 hours to be heat-treated, and pulverized with a press machine (20 MPa, 3 seconds) to obtain a metal oxide composed of alumina. Fiber B4 (average fiber diameter: 0.7 μm, average fiber length: 50 μm) was obtained.
（金属酸化物繊維集合体の調製）
まず、実施例１と同様のシリカ系バインダを調製した。次に、金属酸化物繊維Ａ及びＢ４を質量比９９：１でエタノールに混合し分散させ、分散された分散液を桐山ロートで吸引濾過し、金属酸化物繊維集合体前駆体を調製した。
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度８００℃で２時間焼成して熱処理し、円筒形の金属酸化物繊維集合体を得た。この金属酸化物繊維集合体は、円筒形の形状を保っており、金属酸化物繊維集合体をピンセットで持ち上げたときに、金属酸化物繊維集合体が形崩れを起こさなかった。
(Preparation of metal oxide fiber aggregate)
First, a silica-based binder similar to that in Example 1 was prepared. Next, the metal oxide fibers A and B4 were mixed and dispersed in ethanol at a mass ratio of 99: 1, and the dispersed dispersion was suction-filtered with a Kiriyama funnel to prepare a metal oxide fiber aggregate precursor.
Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was fired at a temperature of 800 ° C. for 2 hours in an air atmosphere to heat-treat it into a cylindrical shape. The metal oxide fiber aggregate of the above was obtained. The metal oxide fiber aggregate maintained a cylindrical shape, and when the metal oxide fiber aggregate was lifted with tweezers, the metal oxide fiber aggregate did not lose its shape.
（実施例８）
（金属酸化物繊維Ａの調製）
実施例１と同様の方法で、金属酸化物繊維Ａを調製した。
(Example 8)
(Preparation of metal oxide fiber A)
The metal oxide fiber A was prepared in the same manner as in Example 1.
（金属酸化物繊維Ｂの調製）
チタンテトラノルマルブトキシド１質量部に、酢酸１．３質量部を添加混合することにより、均一な溶液を調製した。この溶液に対して、イオン交換水１質量部を攪拌しながら添加し、透明な溶液を得た。
次いで、透明な溶液とポリビニルピロリドン溶液（平均分子量：６３００００、固形分濃度：２０ｍａｓｓ％ 、溶媒：Ｎ，Ｎ－ジメチルホルムアミド）とを、質量比で３：２となるように混合して、紡糸液ｂ５を調製した。
次に、得られた紡糸液ｂ５を、静電紡糸法により紡糸するとともに、アースされたドラムに繊維を集積させ、金属酸化物繊維Ｂ５前駆体を形成した。詳細を以下に示す。
紡糸液ｂ５の吐出量：０．５ｇ／時間
ノズル先端とドラム捕集体との距離：１０ｃｍ
紡糸容器内の温湿度：２５℃、３０％ＲＨ
ノズルへの印加電圧：＋１０ｋＶ
次に、得られた金属酸化物繊維Ｂ５前駆体を空気雰囲気下、温度６００℃で２時間焼成して熱処理し、プレス機で粉砕（１０ＭＰａ、３秒間）し、チタニアから構成された金属酸化物繊維Ｂ５（平均繊維径：０．５μｍ、平均繊維長：６０μｍ）を得た。
（金属酸化物繊維集合体の調製）
まず、実施例１と同様のシリカ系バインダを調製した。次に、金属酸化物繊維Ａ及びＢ５を質量比９９：１の割合でエタノールに混合し分散させ、分散された分散液を桐山ロートで吸引濾過し、円筒形の金属酸化物繊維集合体前駆体を調製した。
(Preparation of metal oxide fiber B)
A uniform solution was prepared by adding and mixing 1.3 parts by mass of acetic acid to 1 part by mass of titanium tetranormalbutoxide. To this solution, 1 part by mass of ion-exchanged water was added with stirring to obtain a transparent solution.
Next, a transparent solution and a polyvinylpyrrolidone solution (average molecular weight: 630000, solid content concentration: 20 mass%, solvent: N, N-dimethylformamide) are mixed so as to have a mass ratio of 3: 2, and the spinning solution is used. b5 was prepared.
Next, the obtained spinning liquid b5 was spun by an electrostatic spinning method, and the fibers were accumulated on a grounded drum to form a metal oxide fiber B5 precursor. Details are shown below.
Discharge amount of spinning liquid b5: 0.5 g / hour Distance between nozzle tip and drum collector: 10 cm
Temperature and humidity in the spinning container: 25 ° C, 30% RH
Voltage applied to the nozzle: + 10kV
Next, the obtained metal oxide fiber B5 precursor was calcined in an air atmosphere at a temperature of 600 ° C. for 2 hours to be heat-treated, and pulverized with a press machine (10 MPa, 3 seconds) to obtain a metal oxide composed of titania. Fiber B5 (average fiber diameter: 0.5 μm, average fiber length: 60 μm) was obtained.
(Preparation of metal oxide fiber aggregate)
First, a silica-based binder similar to that in Example 1 was prepared. Next, the metal oxide fibers A and B5 were mixed and dispersed in ethanol at a mass ratio of 99: 1, and the dispersed dispersion was suction-filtered with a Kiriyama funnel to form a cylindrical metal oxide fiber aggregate precursor. Was prepared.
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度６００℃で２時間焼成して熱処理し、円筒形の金属酸化物繊維集合体を得た。この金属酸化物繊維集合体は、円筒形の形状を保っており、金属酸化物繊維集合体をピンセットで持ち上げたときに、金属酸化物繊維集合体が形崩れを起こさなかった。 Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was fired at a temperature of 600 ° C. for 2 hours in an air atmosphere to heat-treat it into a cylindrical shape. The metal oxide fiber aggregate of the above was obtained. The metal oxide fiber aggregate maintained a cylindrical shape, and when the metal oxide fiber aggregate was lifted with tweezers, the metal oxide fiber aggregate did not lose its shape.
（実施例９）
（金属酸化物繊維Ａの調製）
実施例１と同様の方法で、金属酸化物繊維Ａを調製した。
(Example 9)
(Preparation of metal oxide fiber A)
The metal oxide fiber A was prepared in the same manner as in Example 1.
（金属酸化物繊維Ｂの調製）
硝酸ガドリニウム六水和物（１０ｍｍｏｌ）、硝酸セリウム六水和物（９０ｍｍｏｌ）に２－プロパノール１００ｇを加えた後、温度８０℃で１時間加熱撹拌を行い、金属塩を溶解させて、溶液を得た。前記溶液をエバポレータにより、後述する焼成によりＧｄ０
．１Ｃｅ０
．９Ｏ２とした時にＧｄ０．１Ｃｅ０．９Ｏ２が溶液中に３０ｍａｓｓ％含まれる量となるまで濃縮して、濃縮溶液を得た。前記濃縮溶液に、メトキシエチレン無水マレイン酸コポリマーを、焼成によりＧｄ０．１Ｃｅ０．９Ｏ２とした時のＧｄ０．１Ｃｅ０．９Ｏ２質量とメトキシエチレン無水マレイン酸コポリマー質量とを、前記濃縮溶解液に、メトキシエチレン無水マレイン酸コポリマーを、焼成によりＧｄ０．１Ｃｅ０．９Ｏ２とした時のＧｄ０．１Ｃｅ０．９Ｏ２重量とメトキシエチレン無水マレイン酸コポリマー重量とが１：３の割合となるように溶解させ質量比で１：３となるように混合して、紡糸液ｂ６を調製した。
次に、得られた紡糸液ｂ６を、静電紡糸法により紡糸するとともに、アースされたドラムに繊維を集積させ、金属酸化物繊維Ｂ６前駆体を形成した。詳細を以下に示す。
紡糸液ｂ６の吐出量：０．５ｇ／時間
ノズル先端とドラム捕集体との距離：１０ｃｍ
紡糸容器内の温湿度：２５℃、２５％ＲＨ
ノズルへの印加電圧：＋７．５ｋＶ
次に、得られた金属酸化物繊維Ｂ６前駆体を空気雰囲気下、温度６００℃で２時間焼成して熱処理し、適宜粉砕して、Ｇｄ０
．１Ｃｅ０
．９Ｏ２から構成された金属酸化物繊維Ｂ６（平均繊維径：０．２μｍ、平均繊維長：３０μｍ）を得た。
(Preparation of metal oxide fiber B)
After adding 100 g of 2-propanol to gadolinium nitrate hexahydrate (10 mmol) and cerium nitrate hexahydrate (90 mmol), the mixture is heated and stirred at a temperature of 80 ° C. for 1 hour to dissolve the metal salt to obtain a solution. rice field. The solution was subjected to Gd 0. By firing described later with an evaporator . 1 Ce 0 . When it was 9 O 2 , it was concentrated until Gd 0.1 Ce 0.9 O 2 was contained in the solution in an amount of 30 mass% to obtain a concentrated solution. In the concentrated solution, the mass of Gd 0.1 Ce 0.9 O 2 and the mass of the methoxyethylene maleic anhydride copolymer when the methoxyethylene maleic anhydride copolymer was added to Gd 0.1 Ce 0.9 O 2 by firing were added. The weight of Gd 0.1 Ce 0.9 O 2 and the weight of the methoxyethylene maleic anhydride copolymer when the methoxyethylene maleic anhydride copolymer was added to the concentrated solution to Gd 0.1 Ce 0.9 O 2 by firing. And was dissolved so as to have a ratio of 1: 3, and mixed so as to have a mass ratio of 1: 3 to prepare a spinning solution b6.
Next, the obtained spinning liquid b6 was spun by an electrostatic spinning method, and the fibers were accumulated on a grounded drum to form a metal oxide fiber B6 precursor. Details are shown below.
Discharge amount of spinning liquid b6: 0.5 g / hour Distance between nozzle tip and drum collector: 10 cm
Temperature and humidity in the spinning container: 25 ° C, 25% RH
Voltage applied to the nozzle: +7.5 kV
Next, the obtained metal oxide fiber B6 precursor was fired in an air atmosphere at a temperature of 600 ° C. for 2 hours to be heat-treated, and appropriately pulverized to obtain Gd 0 . 1 Ce 0 . A metal oxide fiber B6 (average fiber diameter: 0.2 μm, average fiber length: 30 μm) composed of 9 O 2 was obtained.
（金属酸化物繊維集合体の調製）
まず、実施例１と同様のシリカ系バインダを調製した。次に、金属酸化物繊維Ａ及びＢ６を質量比９９：１でエタノールに混合し分散させ、分散された分散液を桐山ロートで吸引濾過し、円筒形の金属酸化物繊維集合体前駆体を調製した。
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度６００℃で２時間焼成して熱処理し、円筒形の金属酸化物繊維集合体を得た。この金属酸化物繊維集合体は、円筒形の形状を保っており、金属酸化物繊維集合体をピンセットで持ち上げたときに、金属酸化物繊維集合体が形崩れを起こさなかった。
(Preparation of metal oxide fiber aggregate)
First, a silica-based binder similar to that in Example 1 was prepared. Next, the metal oxide fibers A and B6 were mixed and dispersed in ethanol at a mass ratio of 99: 1, and the dispersed dispersion was suction-filtered with a Kiriyama funnel to prepare a cylindrical metal oxide fiber aggregate precursor. did.
Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was fired at a temperature of 600 ° C. for 2 hours in an air atmosphere to heat-treat it into a cylindrical shape. The metal oxide fiber aggregate of the above was obtained. The metal oxide fiber aggregate maintained a cylindrical shape, and when the metal oxide fiber aggregate was lifted with tweezers, the metal oxide fiber aggregate did not lose its shape.
（実施例１０）
（金属酸化物繊維Ａの調製）
実施例１と同様の方法で金属酸化物繊維Ａを調製した。
(Example 10)
(Preparation of metal oxide fiber A)
The metal oxide fiber A was prepared in the same manner as in Example 1.
（金属酸化物繊維Ｂの調製）
メタバナジン（Ｖ）酸アンモニウム（６０ｍｍｏｌ）、及び酢酸リチウム（２０ｍｍｏｌ）を水３５０ｍｌに加えた後、温度８０℃で２時間加熱撹拌を行い、金属塩を溶解させて、溶液を得た。前記溶液に、４０％クエン酸溶液を、溶液のｐＨが３になるまで加えた後、温度８０℃で２時間加熱撹拌を行い、酸性溶液を得た。前記酸性溶液にアンモニア水を、ｐＨが７になるまで加え、中性溶液を得た。前記中性溶液をエバポレータにより、焼成によりＬｉ１．５Ｖ３Ｏ８とした時にＬｉ１．５Ｖ３Ｏ８が中性溶液中に１０ｍａｓｓ％含まれる量となるまで濃縮して、濃縮溶液を得た。前記濃縮溶液に、メトキシエチレン無水マレイン酸コポリマーを、焼成によりＬｉ１．５Ｖ３Ｏ８とした時のＬｉ１．５Ｖ３Ｏ８質量とメトキシエチレン無水マレイン酸コポリマー質量とが１：３の割合となるように溶解させ、紡糸液ｂ７を調製した。
次に、得られた紡糸液ｂ７を、ガスのせん断作用と電界の作用によって紡糸する方法により紡糸して、集積させ、金属酸化物繊維Ｂ７前駆体を形成した。
なお、ガスのせん断作用と電界の作用によって紡糸する方法は、特開２０１２－１５４００９号公報の実施例１と同じ紡糸条件で実施した。詳細を以下に示す。
紡糸液ｂ７の吐出量：０．５ｇ／時間
ガス吐出ノズルからの空気吐出圧力：０．３ＭＰａ
ガス吐出ノズルからの吐出空気温度：２５℃
液吐出ノズル（紡糸ノズル）への印加電圧：８ｋＶ
紡糸室内の雰囲気：温度２５℃、湿度２５％ＲＨ
次に、得られた金属酸化物繊維Ｂ７前駆体を空気雰囲気下、温度４５０℃で２時間焼成して熱処理し、適宜粉砕して、Ｌｉ１．５Ｖ３Ｏ８から構成された金属酸化物繊維Ｂ７（平均繊維径：０．５μｍ、平均繊維長：３０μｍ）を得た。
(Preparation of metal oxide fiber B)
Ammonium metavanazine (V) (60 mmol) and lithium acetate (20 mmol) were added to 350 ml of water, and the mixture was heated and stirred at a temperature of 80 ° C. for 2 hours to dissolve the metal salt to obtain a solution. A 40% citric acid solution was added to the solution until the pH of the solution reached 3, and then heating and stirring were performed at a temperature of 80 ° C. for 2 hours to obtain an acidic solution. Ammonia water was added to the acidic solution until the pH reached 7, to obtain a neutral solution. When the neutral solution is calcined to Li 1.5 V 3 O 8 by an evaporator , the neutral solution is concentrated to an amount of 10 mass% contained in the neutral solution, and the concentrated solution is prepared. Obtained. When the methoxyethylene maleic anhydride copolymer was added to the concentrated solution to Li 1.5 V 3 O 8 by firing, the mass of Li 1.5 V 3 O 8 and the mass of the methoxyethylene maleic anhydride copolymer were 1: 3. The spinning solution b7 was prepared by dissolving the mixture in a ratio.
Next, the obtained spinning liquid b7 was spun by a method of spinning by the shearing action of gas and the action of an electric field and accumulated to form a metal oxide fiber B7 precursor.
The method of spinning by the action of the shearing action of the gas and the action of the electric field was carried out under the same spinning conditions as in Example 1 of JP2012-15409A. Details are shown below.
Discharge amount of spinning liquid b7: 0.5 g / hour Air discharge pressure from gas discharge nozzle: 0.3 MPa
Discharge air temperature from gas discharge nozzle: 25 ° C
Voltage applied to the liquid discharge nozzle (spinning nozzle): 8 kV
Atmosphere in the spinning room: temperature 25 ° C, humidity 25% RH
Next, the obtained metal oxide fiber B7 precursor was fired at a temperature of 450 ° C. for 2 hours in an air atmosphere, heat-treated, and appropriately pulverized to form a metal oxide composed of Li 1.5 V 3 O 8 . Fiber B7 (average fiber diameter: 0.5 μm, average fiber length: 30 μm) was obtained.
（金属酸化物繊維集合体の調製）
まず、実施例１と同様のシリカ系バインダを調製した。次に、金属酸化物繊維Ａ及びＢ７を質量比９９：１の割合でエタノールに混合し分散させ、分散された分散液を桐山ロートで吸引濾過し、円筒形の金属酸化物繊維集合体前駆体を調製した。
(Preparation of metal oxide fiber aggregate)
First, a silica-based binder similar to that in Example 1 was prepared. Next, the metal oxide fibers A and B7 were mixed and dispersed in ethanol at a mass ratio of 99: 1, and the dispersed dispersion was suction-filtered with a Kiriyama funnel to form a cylindrical metal oxide fiber aggregate precursor. Was prepared.
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度４５０℃で２時間焼成して熱処理し、円筒形の金属酸化物繊維集合体を得た。この金属酸化物繊維集合体は、円筒形の形状を保っており、金属酸化物繊維集合体をピンセットで持ち上げたときに、金属酸化物繊維集合体が形崩れを起こさなかった。 Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was fired at a temperature of 450 ° C. for 2 hours in an air atmosphere to heat-treat it into a cylindrical shape. The metal oxide fiber aggregate of the above was obtained. The metal oxide fiber aggregate maintained a cylindrical shape, and when the metal oxide fiber aggregate was lifted with tweezers, the metal oxide fiber aggregate did not lose its shape.
（比較例１）
（金属酸化物繊維Ｂの調製）
実施例１と同様の方法で、金属酸化物繊維Ｂ１を調製した。
(Comparative Example 1)
(Preparation of metal oxide fiber B)
The metal oxide fiber B1 was prepared in the same manner as in Example 1.
（金属酸化物繊維集合体の調製）
まず、実施例１と同様のシリカ系バインダを調製した。次に、金属酸化物繊維Ｂ１のみをエタノールに混合し分散させ、金属酸化物繊維Ｂ１が分散された分散液を桐山ロートで吸引濾過し、円筒形の金属酸化物繊維集合体前駆体を調製した。
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度８００℃で２時間焼成して熱処理し、金属酸化物繊維集合体を得た。しかし、得られた金属酸化物繊維集合体は円筒形状を維持しておらず、また、ピンセットで持ち上げるときに形崩れを起こすものであった。
(Preparation of metal oxide fiber aggregate)
First, a silica-based binder similar to that in Example 1 was prepared. Next, only the metal oxide fiber B1 was mixed and dispersed in ethanol, and the dispersion liquid in which the metal oxide fiber B1 was dispersed was suction-filtered with a Kiriyama funnel to prepare a cylindrical metal oxide fiber aggregate precursor. ..
Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was calcined at a temperature of 800 ° C. for 2 hours in an air atmosphere to heat-treat the metal oxidation. An aggregate of material fibers was obtained. However, the obtained metal oxide fiber aggregate did not maintain a cylindrical shape, and was deformed when lifted with tweezers.
（比較例２）
（金属酸化物繊維Ｂの調製）
実施例７と同様の方法で、金属酸化物繊維Ｂ４を調製した。
(Comparative Example 2)
(Preparation of metal oxide fiber B)
The metal oxide fiber B4 was prepared in the same manner as in Example 7.
（金属酸化物繊維集合体の調製）
まず、実施例１と同様のシリカ系バインダを調製した。次に、金属酸化物繊維Ｂ４をエタノールに混合し分散させ、金属酸化物繊維Ｂ４が分散された分散液を桐山ロートで吸引濾過し、円筒形の金属酸化物繊維集合体前駆体を調製した。
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度８００℃で２時間焼成して熱処理し、金属酸化物繊維集合体を得た。しかし、得られた金属酸化物繊維集合体は円筒形状を維持しておらず、また、ピンセットで持ち上げるときに形崩れを起こすものであった。
(Preparation of metal oxide fiber aggregate)
First, a silica-based binder similar to that in Example 1 was prepared. Next, the metal oxide fiber B4 was mixed with ethanol and dispersed, and the dispersion liquid in which the metal oxide fiber B4 was dispersed was suction-filtered with a Kiriyama funnel to prepare a cylindrical metal oxide fiber aggregate precursor.
Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was calcined at a temperature of 800 ° C. for 2 hours in an air atmosphere to heat-treat the metal oxidation. An aggregate of material fibers was obtained. However, the obtained metal oxide fiber aggregate did not maintain a cylindrical shape, and was deformed when lifted with tweezers.
（比較例３）
（金属酸化物繊維Ｂの調製）
実施例８と同様の方法で、金属酸化物繊維Ｂ５を調製した。
(Comparative Example 3)
(Preparation of metal oxide fiber B)
The metal oxide fiber B5 was prepared in the same manner as in Example 8.
（金属酸化物繊維集合体の調製）
まず、実施例１と同様のシリカ系バインダを調製した。次に、金属酸化物繊維Ｂ５をエタノールに混合し分散させ、金属酸化物繊維Ｂ５が分散された分散液を桐山ロートで吸引濾過し、円筒形の金属酸化物繊維集合体前駆体を調製した。
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度６００℃で２時間焼成して熱処理し、金属酸化物繊維集合体を得た。しかし、得られた金属酸化物繊維集合体は円筒形状を維持しておらず、また、ピンセットで持ち上げるときに形崩れを起こすものであった。
(Preparation of metal oxide fiber aggregate)
First, a silica-based binder similar to that in Example 1 was prepared. Next, the metal oxide fiber B5 was mixed with ethanol and dispersed, and the dispersion liquid in which the metal oxide fiber B5 was dispersed was suction-filtered with a Kiriyama funnel to prepare a cylindrical metal oxide fiber aggregate precursor.
Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was calcined at a temperature of 600 ° C. for 2 hours in an air atmosphere to heat-treat the metal oxidation. An aggregate of material fibers was obtained. However, the obtained metal oxide fiber aggregate did not maintain a cylindrical shape, and was deformed when lifted with tweezers.
（比較例４）
（金属酸化物繊維Ｂの調製）
実施例９と同様の方法で、金属酸化物繊維Ｂ６を調製した。
(Comparative Example 4)
(Preparation of metal oxide fiber B)
The metal oxide fiber B6 was prepared in the same manner as in Example 9.
（金属酸化物繊維集合体の調製）
まず、実施例１と同様のシリカ系バインダを調製した。次に、金属酸化物繊維Ｂ６をエタノールに混合し分散させ、金属酸化物繊維Ｂ６が分散された分散液を桐山ロートで吸引濾過し、円筒形の金属酸化物繊維集合体前駆体を調製した。
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度６００℃で２時間焼成して熱処理し、金属酸化物繊維集合体を得た。しかし、得られた金属酸化物繊維集合体は円筒形状を維持しておらず、また、ピンセットで持ち上げるときに形崩れを起こすものであった。
(Preparation of metal oxide fiber aggregate)
First, a silica-based binder similar to that in Example 1 was prepared. Next, the metal oxide fiber B6 was mixed with ethanol and dispersed, and the dispersion liquid in which the metal oxide fiber B6 was dispersed was suction-filtered with a Kiriyama funnel to prepare a cylindrical metal oxide fiber aggregate precursor.
Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was calcined at a temperature of 600 ° C. for 2 hours in an air atmosphere to heat-treat the metal oxidation. An aggregate of material fibers was obtained. However, the obtained metal oxide fiber aggregate did not maintain a cylindrical shape, and was deformed when lifted with tweezers.
（比較例５）
（金属酸化物繊維Ｂの調製）
実施例１０と同様の方法で、金属酸化物繊維Ｂ７を調製した。
(Comparative Example 5)
(Preparation of metal oxide fiber B)
The metal oxide fiber B7 was prepared in the same manner as in Example 10.
（金属酸化物繊維集合体の調製）
まず、実施例１と同様のシリカ系バインダを調製した。次に、金属酸化物繊維Ｂ７をエタノールに混合し分散させ、金属酸化物繊維Ｂ７が分散された分散液を桐山ロートで吸引濾過し、円筒形の金属酸化物繊維集合体前駆体を調製した。
次に、シリカ系バインダを金属酸化物繊維集合体前駆体に塗布して、桐山ロートで吸引濾過し、得られたものを空気雰囲気下、温度４５０℃で２時間焼成して熱処理し、金属酸化物繊維集合体を得た。しかし、得られた金属酸化物繊維集合体は円筒形状を維持しておらず、また、ピンセットで持ち上げるときに形崩れを起こすものであった。
(Preparation of metal oxide fiber aggregate)
First, a silica-based binder similar to that in Example 1 was prepared. Next, the metal oxide fiber B7 was mixed with ethanol and dispersed, and the dispersion liquid in which the metal oxide fiber B7 was dispersed was suction-filtered with a Kiriyama funnel to prepare a cylindrical metal oxide fiber aggregate precursor.
Next, a silica-based binder was applied to the metal oxide fiber aggregate precursor, suction-filtered with a Kiriyama funnel, and the obtained product was calcined at a temperature of 450 ° C. for 2 hours in an air atmosphere to heat-treat the metal oxidation. An aggregate of material fibers was obtained. However, the obtained metal oxide fiber aggregate did not maintain a cylindrical shape, and was deformed when lifted with tweezers.
以上のことから、実施例の構成を満たす、金属酸化物繊維Ａ及び金属酸化物繊維Ｂを有する金属酸化物繊維集合体は、ピンセットで持ち上げても形崩れを起こさない金属酸化物繊維集合体であった。 From the above, the metal oxide fiber aggregate having the metal oxide fiber A and the metal oxide fiber B satisfying the constitution of the embodiment is a metal oxide fiber aggregate that does not lose its shape even when lifted with tweezers. there were.
本発明の金属酸化物繊維集合体は、形崩れを起こさず取り扱い性に優れるため、触媒や、熱伝導性部材など様々な用途に用いることができる。 Since the metal oxide fiber aggregate of the present invention does not lose its shape and is excellent in handleability, it can be used for various purposes such as a catalyst and a heat conductive member.
Claims (5)
シリカ以外の金属酸化物を主体とする金属酸化物繊維Ｂを含む、
金属酸化物繊維集合体。 Metal oxide fiber A mainly composed of silica and
Containing metal oxide fiber B mainly composed of metal oxides other than silica,
Metal oxide fiber aggregate.
（ｉｉ）紡糸液ａを紡糸し焼成することで、シリカを主体とする金属酸化物繊維Ａを調製する工程、
（ｉｉｉ）紡糸液ｂを紡糸し焼成することで、シリカ以外の金属酸化物を主体とする金属酸化物繊維Ｂを調製する工程、
（ｉｖ）金属酸化物繊維Ａと金属酸化物繊維Ｂを混合し、金属酸化物繊維集合体を調製する工程、
を含む、請求項１～３のいずれか１項に記載の金属酸化物繊維集合体の製造方法。 (I) A step of preparing a spinning liquid a containing a substance containing silicon and a spinning liquid b containing a substance containing a metal other than silicon.
(Ii) A step of preparing a metal oxide fiber A mainly composed of silica by spinning and firing a spinning liquid a.
(Iii) A step of preparing a metal oxide fiber B mainly composed of a metal oxide other than silica by spinning and firing the spinning liquid b.
(Iv) A step of mixing a metal oxide fiber A and a metal oxide fiber B to prepare a metal oxide fiber aggregate.
The method for producing a metal oxide fiber aggregate according to any one of claims 1 to 3, which comprises.
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