JP2013071859A - Method for producing vanadium dioxide particle - Google Patents
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本発明は、適度な粒子径を有し、高純度の二酸化バナジウム粒子を作製することが可能な二酸化バナジウム粒子の製造方法に関する。 The present invention relates to a method for producing vanadium dioxide particles having an appropriate particle size and capable of producing high-purity vanadium dioxide particles.
二酸化バナジウムは、温度変化によって透過率や反射率等の光学的特性が可逆的に変化するサーモクロミック現象を示す材料として注目されている。ルチル型二酸化バナジウムの結晶は、相転移温度以下では半導体相を示すが、相転移温度以上では金属相へ転移する。相転移は約６８℃で可逆的に起こり、近赤外線及び赤外線透過率が大幅に変化する。
このような性質を利用して、相転移温度以下では、可視光線、赤外線ともに透過するが、相転移温度を超えると可視光線のみを透過して、赤外線を遮断するという特性を発現する赤外線遮断材として用いることが提案されている。
Vanadium dioxide has attracted attention as a material exhibiting a thermochromic phenomenon in which optical characteristics such as transmittance and reflectance are reversibly changed by temperature change. The crystal of rutile vanadium dioxide exhibits a semiconductor phase below the phase transition temperature, but transitions to the metal phase above the phase transition temperature. The phase transition occurs reversibly at about 68 ° C., and the near-infrared and infrared transmittance changes significantly.
Utilizing these properties, both infrared rays and infrared rays are transmitted below the phase transition temperature, but only visible rays are transmitted when the phase transition temperature is exceeded. It has been proposed to be used as
特許文献１には、バナジウムアルコキシドと、モリブデン又はタングステンアルコキシドとをイソプロパノールに溶解した後、イオン交換水を添加して加水分解反応させ、焼成することで金属ドープ二酸化バナジウムを作製する方法が提案されている。
しかしながら、特許文献１の方法では、加水分解反応条件が促進されず、収率が低くなるという問題があった。
Patent Document 1 proposes a method for producing metal-doped vanadium dioxide by dissolving vanadium alkoxide and molybdenum or tungsten alkoxide in isopropanol, then adding ion-exchanged water to cause a hydrolysis reaction, and firing. Yes.
However, the method of Patent Document 1 has a problem that the hydrolysis reaction conditions are not accelerated and the yield is low.
更に、特許文献２には、バナジウム化合物含有溶液に、一部がルチル型結晶相からなる二酸化チタンの粒子を添加し、水熱反応させることにより、Ｒ相の二酸化バナジウムを製造する方法が開示されている。
しかしながら、この方法では、二酸化チタン粒子上に二酸化バナジウムが成長するため、二酸化バナジウムのみを単離、利用することは困難であるという問題点があった。
Further, Patent Document 2 discloses a method for producing R-phase vanadium dioxide by adding titanium dioxide particles partially composed of a rutile-type crystal phase to a vanadium compound-containing solution and causing a hydrothermal reaction. ing.
However, this method has a problem in that it is difficult to isolate and use only vanadium dioxide because vanadium dioxide grows on the titanium dioxide particles.
本発明は、適度な粒子径を有し、高純度の二酸化バナジウム粒子を作製することが可能な二酸化バナジウム粒子の製造方法を提供することを目的とする。 An object of this invention is to provide the manufacturing method of the vanadium dioxide particle which has a moderate particle diameter and can produce a highly purified vanadium dioxide particle.
本発明は、バナジウムアルコキシド及びアルコールを含有するバナジウムアルコキシド溶液と、塩基性水溶液とを反応させ、酸化バナジウム前駆体を含有する溶液を作製する反応工程、前記酸化バナジウム前駆体を焼成する焼成工程、及び、前記焼成した酸化バナジウム前駆体を水素雰囲気中で還元する還元工程を有し、前記反応工程において、ｐＨ１０．９〜１２．５の範囲内で反応を行い、かつ、前記還元工程において、６００〜６５０℃で１０〜３０分間、又は、５００〜５５０℃で１〜２時間の条件で還元を行う二酸化バナジウム粒子の製造方法である。
以下、本発明を詳述する。
The present invention comprises a reaction step of reacting a vanadium alkoxide solution containing vanadium alkoxide and alcohol with a basic aqueous solution to produce a solution containing a vanadium oxide precursor, a firing step of firing the vanadium oxide precursor, and And a reduction step of reducing the calcined vanadium oxide precursor in a hydrogen atmosphere, in the reaction step, the reaction is performed within a pH range of 10.9 to 12.5, and in the reduction step, 600 to It is the manufacturing method of the vanadium dioxide particle which reduces on conditions for 650 degreeC for 10 to 30 minutes, or 500 to 550 degreeC for 1 to 2 hours.
The present invention is described in detail below.
本発明者は、鋭意検討した結果、バナジウムアルコキシド溶液と、塩基性水溶液とを反応させる際のｐＨを所定の範囲内とし、かつ、還元工程での温度、時間を調整することで、二酸化バナジウムの比率が高く高純度であり、かつ、適度な粒子径を有する二酸化バナジウム粒子が得られることを見出し、本発明を完成させるに至った。 As a result of intensive studies, the present inventor made the pH at the time of reacting the vanadium alkoxide solution and the basic aqueous solution within a predetermined range, and by adjusting the temperature and time in the reduction step, the vanadium dioxide It has been found that vanadium dioxide particles having a high ratio and high purity and having an appropriate particle diameter can be obtained, and the present invention has been completed.
本発明の二酸化バナジウム粒子の製造方法では、バナジウムアルコキシド及びアルコールを含有するバナジウムアルコキシド溶液と、塩基性水溶液とを反応させ、酸化バナジウム前駆体を含有する溶液を作製する反応工程を有する。
なお、酸化バナジウム前駆体とは、五価のバナジウムの酸化物が主に含まれる酸化バナジウムをいう。
In the manufacturing method of the vanadium dioxide particle of this invention, it has the reaction process which makes the vanadium alkoxide solution containing vanadium alkoxide and alcohol and basic aqueous solution react, and produces the solution containing a vanadium oxide precursor.
The vanadium oxide precursor refers to vanadium oxide mainly containing pentavalent vanadium oxide.
本発明では、上記反応工程において、ｐＨ１０．９〜１２．５の範囲内で反応を行う。
これにより、加水分解反応が促進かつ安定し、酸化バナジウム前駆体の生成も改善され、生成する二酸化バナジウム粒子の収率も向上する。上記ｐＨが１０．９未満であると、加水分解反応が促進せず、酸化バナジウム前駆体の収率が低くなる。一方、ｐＨが１２．５を超えると、加水分解反応が安定せず、酸化バナジウム前駆体の収率が低くなる。好ましくは１０．９〜１２．０、より好ましくは１０．９〜１１．７である。
In the present invention, in the reaction step, the reaction is performed within a pH range of 10.9 to 12.5.
As a result, the hydrolysis reaction is accelerated and stabilized, the production of the vanadium oxide precursor is improved, and the yield of the vanadium dioxide particles to be produced is also improved. When the pH is less than 10.9, the hydrolysis reaction is not accelerated and the yield of the vanadium oxide precursor is lowered. On the other hand, when the pH exceeds 12.5, the hydrolysis reaction is not stable, and the yield of the vanadium oxide precursor is lowered. Preferably it is 10.9-12.0, More preferably, it is 10.9-11.7.
上記反応工程において、ｐＨ１０．９〜１２．５の範囲内に調整する方法としては、アルカリ性材料を任意に添加し、反応系をアルカリ性ｐＨ環境とする方法等が挙げられる。 Examples of the method for adjusting the pH within the range of 10.9 to 12.5 in the reaction step include a method in which an alkaline material is arbitrarily added and the reaction system is set to an alkaline pH environment.
上記バナジウムアルコキシドとしては、例えば、バナジウムトリイソプロポキシドオキシド、バナジウムトリノルマルプロポキシドオキシド、バナジウムトリメトキシドオキシド、バナジウムトリエトキシドオキシド等が挙げられる。 Examples of the vanadium alkoxide include vanadium triisopropoxide oxide, vanadium trinormal propoxide oxide, vanadium trimethoxide oxide, vanadium triethoxide oxide, and the like.
上記アルコールとしては特に限定されないが、例えば、イソプロパノール、エタノール、メタノール、ブタノール等が挙げられる。 Although it does not specifically limit as said alcohol, For example, isopropanol, ethanol, methanol, a butanol etc. are mentioned.
上記バナジウムアルコキシド溶液における上記バナジウムアルコキシドの含有量は、１〜１０重量％であることが好ましい。上記範囲内とすることで、加水分解反応も制御しやすく、生成する二酸化バナジウム粒子の収率も向上する。 The vanadium alkoxide content in the vanadium alkoxide solution is preferably 1 to 10% by weight. By setting it within the above range, the hydrolysis reaction can be easily controlled, and the yield of the generated vanadium dioxide particles can be improved.
上記塩基性水溶液としては、アンモニア、水酸化ナトリウム等の水溶液が好ましい。
なかでも、乾燥又は焼成中に脱離しやすく粒子に残存しないという理由から、アンモニアが好ましい。
As the basic aqueous solution, an aqueous solution of ammonia, sodium hydroxide or the like is preferable.
Among these, ammonia is preferable because it is easily detached during drying or baking and does not remain in the particles.
上記反応工程における上記アンモニアの添加量は、バナジウムアルコキシドに対して２〜４０重量％であることが好ましい。２重量％未満であると、ｐＨ１０．９以上に調整するのが困難となり、４０重量％を超えると、ｐＨ１２．５以下に調整するのが困難となる。 The amount of ammonia added in the reaction step is preferably 2 to 40% by weight with respect to the vanadium alkoxide. If it is less than 2% by weight, it is difficult to adjust to pH 10.9 or more, and if it exceeds 40% by weight, it is difficult to adjust to pH 12.5 or less.
上記反応工程における反応温度は１０〜８０℃が好ましい。
また、上記反応工程における反応時間は、１〜１２０時間が好ましい。
The reaction temperature in the reaction step is preferably 10 to 80 ° C.
The reaction time in the reaction step is preferably 1 to 120 hours.
本発明では、次いで、上記酸化バナジウム前駆体を焼成する焼成工程を行う。
上記焼成工程における、焼成温度としては、４００℃以上であることが好ましく、４００〜５００℃がより好ましい。また、上記焼成工程においては、例えば、水素雰囲気下又は水素気流中で焼成を行ってもよい。また、上記焼成工程における焼成時間は、１〜５時間とすることが好ましい。
Next, in the present invention, a firing step of firing the vanadium oxide precursor is performed.
As a baking temperature in the said baking process, it is preferable that it is 400 degreeC or more, and 400-500 degreeC is more preferable. Moreover, in the said baking process, you may bake in a hydrogen atmosphere or a hydrogen stream, for example. Moreover, it is preferable that the baking time in the said baking process shall be 1 to 5 hours.
本発明では、その後、上記焼成した酸化バナジウム前駆体を水素雰囲気中で還元する還元工程を行う。
上記還元工程を行うことで、上記五価のバナジウムの酸化物（Ｖ２Ｏ５）が含まれる酸化バナジウム前駆体が、還元され、四価の二酸化バナジウム（ＶＯ２）とすることができる。
In the present invention, after that, a reduction step of reducing the calcined vanadium oxide precursor in a hydrogen atmosphere is performed.
By performing the reduction step, the vanadium oxide precursor containing the pentavalent vanadium oxide (V 2 O 5 ) can be reduced to tetravalent vanadium dioxide (VO 2 ).
上記還元工程は、還元が進みすぎず効率的に二酸化バナジウムを得るという観点から、
（１）水素雰囲気中、６００〜６５０℃で１０〜３０分間の条件、又は、
（２）水素雰囲気中、５００〜５５０℃で１〜２時間の条件、で行う。
From the viewpoint that the reduction process efficiently obtains vanadium dioxide without excessive reduction,
(1) Conditions in a hydrogen atmosphere at 600 to 650 ° C. for 10 to 30 minutes, or
(2) Perform in a hydrogen atmosphere at 500 to 550 ° C. for 1 to 2 hours.
上記条件（１）で還元工程を行うことで、結晶性の高い二酸化バナジウムが得られる。
上記条件（１）では、６００〜６３０℃が好ましく、１５〜３０分間の条件で還元工程を行うことが好ましい。
By performing the reduction step under the above condition (1), highly crystalline vanadium dioxide can be obtained.
In the said condition (1), 600-630 degreeC is preferable and it is preferable to perform a reduction | restoration process on the conditions for 15-30 minutes.
上記条件（２）で還元工程を行うことで、還元が進みすぎず純度の高い二酸化バナジウムが得られる。
上記条件（２）では、５２０〜５５０℃が好ましく、６０〜１２０分間の条件で還元工程を行うことが好ましい。
By performing the reduction step under the above condition (2), vanadium dioxide having high purity can be obtained without excessive reduction.
In said condition (2), 520-550 degreeC is preferable and it is preferable to perform a reduction | restoration process on the conditions for 60 to 120 minutes.
上記還元工程は、上述した水素雰囲気中で行うことが好ましいが、メタン、アンモニア、ブタジエン等の還元ガス雰囲気下で行ってもよい。 The reduction step is preferably performed in the hydrogen atmosphere described above, but may be performed in a reducing gas atmosphere such as methane, ammonia, or butadiene.
本発明の製造方法を用いることで、粒子中の二酸化バナジウムの比率が高く、サーモクロミック性に優れるものとすることができる。
このことは、例えば、粉末Ｘ線回折（ＸＲＤ）を用いて測定することで評価することができる。
また、本発明の製造方法で得られた二酸化バナジウム粒子は、平均粒子径が０．１〜５μｍであることから、これをサーモクロミックフィルム等に用いた場合、薄膜化、大型化が容易で、かつ、高い可視光透過性を有するサーモクロミックフィルムを作製することができる。
By using the production method of the present invention, the ratio of vanadium dioxide in the particles is high, and the thermochromic property can be excellent.
This can be evaluated, for example, by measuring using powder X-ray diffraction (XRD).
In addition, since the vanadium dioxide particles obtained by the production method of the present invention have an average particle size of 0.1 to 5 μm, when this is used for a thermochromic film or the like, it is easy to reduce the thickness and size, In addition, a thermochromic film having high visible light permeability can be produced.
本発明の二酸化バナジウム粒子の製造方法によれば、適度な粒子径を有し、高純度の二酸化バナジウム粒子を作製することが可能となる。 According to the method for producing vanadium dioxide particles of the present invention, high-purity vanadium dioxide particles having an appropriate particle diameter can be produced.
以下に実施例を掲げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Examples of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
（実施例１）
［酸化バナジウム溶液の調製］
バナジウム（Ｖ）トリ−ｉ−プロポキシドオキシド（高純度化学研究所社製）２．５０ｇとイソプロパノール（和光純薬工業社製）７１．２０ｇとを混合し、バナジウムアルコキシド含有溶液を調製した。
また、純水２．５６ｇと２５％アンモニア水溶液（和光純薬工業社製）０．２５ｇを混合し、塩基性水溶液を調製した。得られた塩基性水溶液をバナジウムアルコキシド含有溶液に添加した。
この時の混合液のｐＨは１０．９０であった。その後、室温で２４時間反応させ、酸化バナジウム溶液を得た。
Example 1
[Preparation of vanadium oxide solution]
A vanadium alkoxide-containing solution was prepared by mixing 2.50 g of vanadium (V) tri-i-propoxide oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and 71.20 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.).
Further, 2.56 g of pure water and 0.25 g of 25% aqueous ammonia solution (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed to prepare a basic aqueous solution. The obtained basic aqueous solution was added to the vanadium alkoxide-containing solution.
The pH of the mixed solution at this time was 10.90. Then, it was made to react at room temperature for 24 hours, and the vanadium oxide solution was obtained.
［酸化バナジウム粒子の作製］
得られた酸化バナジウム溶液をエバポレーターによって脱溶媒し、得られた固形物を乾燥させ酸化バナジウム前駆体を得た。得られた酸化バナジウム前駆体を大気中４００℃で２時間焼成した。
その後、窒素／水素（３％）混合ガス気流中、６００℃で３０分間還元することで酸化バナジウム粒子を得た。
[Production of vanadium oxide particles]
The obtained vanadium oxide solution was desolvated with an evaporator, and the obtained solid was dried to obtain a vanadium oxide precursor. The obtained vanadium oxide precursor was calcined in the atmosphere at 400 ° C. for 2 hours.
Thereafter, vanadium oxide particles were obtained by reduction at 600 ° C. for 30 minutes in a nitrogen / hydrogen (3%) mixed gas stream.
（実施例２）
［酸化バナジウム溶液の調製］
純水２．３８ｇと２５％アンモニア水溶液０．５ｇとを混合して塩基性水溶液を調製した以外は実施例１と同様にして、酸化バナジウム溶液を得た。なお、混合液のｐＨは１１．７であった。
(Example 2)
[Preparation of vanadium oxide solution]
A vanadium oxide solution was obtained in the same manner as in Example 1 except that 2.38 g of pure water and 0.5 g of 25% aqueous ammonia solution were mixed to prepare a basic aqueous solution. The pH of the mixed solution was 11.7.
［酸化バナジウム粒子の作製］
得られた酸化バナジウム溶液をエバポレーターによって脱溶媒し、得られた固形物を乾燥させ酸化バナジウム前駆体を得た。得られた酸化バナジウム前駆体を大気中４００℃で２時間焼成した。
その後、窒素／水素（３％）混合ガス気流中、６００℃で３０分間還元することで酸化バナジウム粒子を得た。
[Production of vanadium oxide particles]
The obtained vanadium oxide solution was desolvated with an evaporator, and the obtained solid was dried to obtain a vanadium oxide precursor. The obtained vanadium oxide precursor was calcined in the atmosphere at 400 ° C. for 2 hours.
Thereafter, vanadium oxide particles were obtained by reduction at 600 ° C. for 30 minutes in a nitrogen / hydrogen (3%) mixed gas stream.
（実施例３）
実施例２の［酸化バナジウム粒子の作製］において、６００℃で１５分間還元した以外は実施例２と同様にして酸化バナジウム溶液及び酸化バナジウム粒子を得た。
(Example 3)
In [Production of vanadium oxide particles] in Example 2, a vanadium oxide solution and vanadium oxide particles were obtained in the same manner as in Example 2 except that reduction was performed at 600 ° C. for 15 minutes.
（実施例４）
実施例２の［酸化バナジウム粒子の作製］において、５２５℃で２時間還元した以外は実施例２と同様にして酸化バナジウム溶液及び酸化バナジウム粒子を得た。
Example 4
In [Production of vanadium oxide particles] in Example 2, a vanadium oxide solution and vanadium oxide particles were obtained in the same manner as in Example 2 except that the reduction was performed at 525 ° C. for 2 hours.
（実施例５）
実施例１の［酸化バナジウム溶液の調製］において、純水１．６３ｇと２５％アンモニア水溶液１．５ｇとを混合して塩基性水溶液を調製した以外は実施例１と同様にして、酸化バナジウム溶液及び酸化バナジウム粒子を得た。なお、混合液のｐＨは１２．１７であった。
(Example 5)
A vanadium oxide solution was prepared in the same manner as in Example 1 except that a basic aqueous solution was prepared by mixing 1.63 g of pure water and 1.5 g of a 25% aqueous ammonia solution in [Preparation of vanadium oxide solution] in Example 1. And vanadium oxide particles were obtained. The pH of the mixed solution was 12.17.
（実施例６）
実施例１の［酸化バナジウム溶液の調製］において、純水０．０１ｇと２５％アンモニア水溶液３．６５ｇとを混合して塩基性水溶液を調製した以外は実施例１と同様にして、酸化バナジウム溶液及び酸化バナジウム粒子を得た。なお、混合液のｐＨは１２．４９であった。
(Example 6)
A vanadium oxide solution was prepared in the same manner as in Example 1 except that a basic aqueous solution was prepared by mixing 0.01 g of pure water and 3.65 g of a 25% aqueous ammonia solution in [Preparation of vanadium oxide solution] in Example 1. And vanadium oxide particles were obtained. The pH of the mixed solution was 12.49.
（比較例１）
実施例１の［酸化バナジウム溶液の調製］において、純水２．７４ｇと２５％アンモニア水溶液０．０１ｇとを混合して塩基性水溶液を調製した以外は実施例１と同様にして、酸化バナジウム溶液及び酸化バナジウム粒子を得た。なお、混合液のｐＨは９．８０であった。
(Comparative Example 1)
A vanadium oxide solution was prepared in the same manner as in Example 1 except that a basic aqueous solution was prepared by mixing 2.74 g of pure water and 0.01 g of a 25% aqueous ammonia solution in [Preparation of vanadium oxide solution] in Example 1. And vanadium oxide particles were obtained. The pH of the mixed solution was 9.80.
（比較例２）
実施例１の［酸化バナジウム溶液の調製］において、アンモニア水溶液を加えず、塩基性水溶液に代えて純水２．７５ｇを用いた以外は実施例１と同様にして、酸化バナジウム溶液及び酸化バナジウム粒子を得た。なお、混合液のｐＨは６．５０であった。
(Comparative Example 2)
In [Preparation of vanadium oxide solution] in Example 1, vanadium oxide solution and vanadium oxide particles were added in the same manner as in Example 1 except that 2.75 g of pure water was used instead of the basic aqueous solution without adding the aqueous ammonia solution. Got. The pH of the mixed solution was 6.50.
（比較例３）
実施例１の［酸化バナジウム溶液の調製］において、純水２．７５ｇと酢酸１．５ｇとを混合して酸性水溶液を調製した以外は実施例１と同様にして、酸化バナジウム溶液及び酸化バナジウム粒子を得た。なお、混合液のｐＨは３．９３であった。
(Comparative Example 3)
In [Preparation of vanadium oxide solution] in Example 1, vanadium oxide solution and vanadium oxide particles were prepared in the same manner as in Example 1 except that 2.75 g of pure water and 1.5 g of acetic acid were mixed to prepare an acidic aqueous solution. Got. The pH of the mixed solution was 3.93.
（比較例４）
実施例１の［酸化バナジウム溶液の調製］において、純水２．７５ｇと塩酸１．５ｇとを混合して酸性水溶液を調製した以外は実施例１と同様にして、酸化バナジウム溶液及び酸化バナジウム粒子を得た。なお、混合液のｐＨは１．９２であった。
(Comparative Example 4)
In [Preparation of vanadium oxide solution] in Example 1, vanadium oxide solution and vanadium oxide particles were prepared in the same manner as in Example 1 except that 2.75 g of pure water and 1.5 g of hydrochloric acid were mixed to prepare an acidic aqueous solution. Got. The pH of the mixed solution was 1.92.
（比較例５）
実施例１の［酸化バナジウム粒子の作製］において、６００℃で１時間還元した以外は実施例１と同様にして、酸化バナジウム溶液及び酸化バナジウム粒子を得た。
(Comparative Example 5)
In [Production of vanadium oxide particles] in Example 1, a vanadium oxide solution and vanadium oxide particles were obtained in the same manner as in Example 1 except that reduction was performed at 600 ° C. for 1 hour.
（比較例６）
実施例１の［酸化バナジウム粒子の作製］において、５５０℃で３時間還元した以外は実施例１と同様にして、酸化バナジウム溶液及び酸化バナジウム粒子を得た。
(Comparative Example 6)
In [Production of vanadium oxide particles] in Example 1, a vanadium oxide solution and vanadium oxide particles were obtained in the same manner as in Example 1 except that reduction was performed at 550 ° C. for 3 hours.
（比較例７）
実施例１の［酸化バナジウム粒子の作製］において、５００℃で０．５時間還元した以外は実施例１と同様にして、酸化バナジウム溶液及び酸化バナジウム粒子を得た。
(Comparative Example 7)
In [Production of vanadium oxide particles] in Example 1, a vanadium oxide solution and vanadium oxide particles were obtained in the same manner as in Example 1 except that reduction was performed at 500 ° C. for 0.5 hour.
（評価方法） (Evaluation method)
（１）反応後溶液の安定性
実施例及び比較例で得られた酸化バナジウム溶液５．０ｇに、１．０ｇの水を滴下した後の変色を目視にて確認した。なお、変色がない場合を「安定」、変色があった場合を「不安定」とした。
(1) Stability of solution after reaction The discoloration after 1.0 g of water was dropped into 5.0 g of the vanadium oxide solution obtained in Examples and Comparative Examples was visually confirmed. The case where there was no discoloration was defined as “stable”, and the case where there was discoloration was defined as “unstable”.
（２）二酸化バナジウム生成
実施例及び比較例で得られた酸化バナジウム粒子をＸＲＤ（Ｒｉｇａｋｕ社製、ＲＩＮＴ１０００）を用い、Ｘ線回折法で結晶構造の特定を行った。なお、測定条件は、電圧５０ＫＶ、電流１００ｍＡ、スキャン速度４°／ｍｉｎ、回折角２θ＝１０〜７０°とした。
ＶＯ２のピーク［（０１１）面、２θ＝２７．８°］が確認された場合を「○」、確認されない場合を「×」とした。
(2) Vanadium dioxide production The crystal structure of the vanadium oxide particles obtained in Examples and Comparative Examples was specified by X-ray diffraction using XRD (Rigaku, RINT1000). The measurement conditions were a voltage of 50 KV, a current of 100 mA, a scanning speed of 4 ° / min, and a diffraction angle 2θ = 10 to 70 °.
The case where the peak of VO 2 [(011) plane, 2θ = 27.8 °] was confirmed was “◯”, and the case where it was not confirmed was “x”.
（３）二酸化バナジウム粒子の粒子径
粒度分布計（日機装社製、マイクロトラックＵＡＭ−１）を用いて、反応液後の二酸化バナジウム粒子の分散径（体積平均粒子径）を測定した。
(3) The dispersion diameter (volume average particle diameter) of the vanadium dioxide particles after the reaction solution was measured using a particle size distribution meter (manufactured by Nikkiso Co., Ltd., Microtrac UAM-1).
（４）サーモクロミック性
得られた二酸化バナジウム粒子の相転移時の熱量ΔＨ（ｍＪ／ｍｇ）を、示差走査熱量計ＤＳＣ（エスアイアイ・ナノテクノロジー社製「ＤＳＣ６２２０」）を用い０℃〜１００℃までの温度範囲、昇温速度５℃／ｍｉｎ、窒素雰囲気下にて測定した。
(4) Thermochromic The amount of heat ΔH (mJ / mg) at the phase transition of the obtained vanadium dioxide particles was measured at 0 ° C. to 100 ° C. using a differential scanning calorimeter DSC (“DSC 6220” manufactured by SII Nanotechnology). Up to a temperature range up to 5 ° C./min and a nitrogen atmosphere.
本発明によれば、適度な粒子径を有し、高純度の二酸化バナジウム粒子を作製することが可能な二酸化バナジウム粒子の製造方法を提供することができる。
なお、本発明で得られた二酸化バナジウム粒子は、サーモクロミック性フィルム、合わせガラス用中間膜、合わせガラス及び貼り付け用フィルム等に使用することができる。
ADVANTAGE OF THE INVENTION According to this invention, it can provide the manufacturing method of the vanadium dioxide particle which has moderate particle diameter and can produce a highly purified vanadium dioxide particle.
In addition, the vanadium dioxide particle obtained by this invention can be used for a thermochromic film, the intermediate film for laminated glasses, a laminated glass, a film for affixing, etc.
Claims (3)
前記酸化バナジウム前駆体を焼成する焼成工程、及び、
前記焼成した酸化バナジウム前駆体を水素雰囲気中で還元する還元工程を有し、
前記反応工程において、ｐＨ１０．９〜１２．５の範囲内で反応を行い、かつ、
前記還元工程において、６００〜６５０℃で１０〜３０分間、又は、５００〜５５０℃で１〜２時間の条件で還元を行う
ことを特徴とする二酸化バナジウム粒子の製造方法。 A reaction step of reacting a vanadium alkoxide solution containing vanadium alkoxide and alcohol with a basic aqueous solution to produce a solution containing a vanadium oxide precursor;
A firing step of firing the vanadium oxide precursor; and
A reduction step of reducing the calcined vanadium oxide precursor in a hydrogen atmosphere;
In the reaction step, the reaction is performed within a pH range of 10.9 to 12.5, and
In the reduction step, the reduction is performed under conditions of 600 to 650 ° C for 10 to 30 minutes or 500 to 550 ° C for 1 to 2 hours.
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