JP2016166294A - Method of producing vanadium oxide-containing particle and vanadium oxide-containing particle - Google Patents
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- 239000002245 particle Substances 0.000 title claims abstract description 161
- 229910001935 vanadium oxide Inorganic materials 0.000 title claims abstract description 97
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title abstract description 10
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 64
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 55
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 34
- 238000004519 manufacturing process Methods 0.000 claims description 31
- 238000009826 distribution Methods 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 230000001186 cumulative effect Effects 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 5
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 4
- -1 hydrazine compound Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 35
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 31
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 31
- 239000007864 aqueous solution Substances 0.000 description 27
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 24
- 238000002834 transmittance Methods 0.000 description 17
- 238000000108 ultra-filtration Methods 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- 238000000354 decomposition reaction Methods 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000003814 drug Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本発明は、酸化バナジウム含有粒子の製造方法及び酸化バナジウム含有粒子に関する。より詳しくは、サーモクロミック性及び光透過性に優れた酸化バナジウム含有粒子の製造方法及び酸化バナジウム含有粒子に関する。 The present invention relates to a method for producing vanadium oxide-containing particles and vanadium oxide-containing particles. More specifically, the present invention relates to a method for producing vanadium oxide-containing particles having excellent thermochromic properties and light transmissivity, and vanadium oxide-containing particles.
二酸化バナジウム（ＶＯ２）粒子は、温度変化によって光吸収率や光反射率等の光学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。
ここで、二酸化バナジウム粒子の結晶構造には、Ａ相、Ｂ相、Ｃ相及びＲ相（いわゆる「ルチル型の結晶相」のことをいう。）など、いくつかの結晶相の多形が存在する。この中でも、前述のようなサーモクロミック現象を示す結晶構造は、Ｒ相に限られる。このＲ相は、転移温度以下では、単斜晶系（ｍｏｎｏｃｌｉｎｉｃ）の構造を有するため、Ｍ相とも呼ばれている。このような二酸化バナジウム粒子において、実質的に優良なサーモクロミック性を発現させるためには、二酸化バナジウム粒子が凝集していないこと、平均粒径がナノメートルオーダーであること、粒子が等方的な形状を有していることが望ましい。
Vanadium dioxide (VO 2 ) particles have attracted attention as a material exhibiting a thermochromic phenomenon in which optical properties such as light absorption rate and light reflectance change reversibly with temperature.
Here, in the crystal structure of vanadium dioxide particles, there are several polymorphs of crystal phases such as A phase, B phase, C phase and R phase (so-called “rutile-type crystal phase”). To do. Among these, the crystal structure showing the thermochromic phenomenon as described above is limited to the R phase. Since this R phase has a monoclinic structure below the transition temperature, it is also called an M phase. In such vanadium dioxide particles, in order to exhibit substantially excellent thermochromic properties, vanadium dioxide particles are not aggregated, the average particle size is on the order of nanometers, and the particles are isotropic. It is desirable to have a shape.
このような粒子を作製する技術として、水熱合成法が報告されている（例えば、特許文献１参照。）。
また、二酸化バナジウム粒子の優れたサーモクロミック性と、当該二酸化バナジウム粒子を添加したフィルムの可視光領域における光透過性とを得るためには、可能な限り粒径は均一で、かつ小さくする必要があり、これを解決する手段として、微粒子を添加して粒径をサブミクロン以下にする技術も報告されている（例えば、特許文献２参照。）。
A hydrothermal synthesis method has been reported as a technique for producing such particles (see, for example, Patent Document 1).
Further, in order to obtain the excellent thermochromic property of vanadium dioxide particles and the light transmittance in the visible light region of the film to which the vanadium dioxide particles are added, it is necessary to make the particle size as uniform and as small as possible. As a means for solving this problem, a technique of adding fine particles to reduce the particle size to submicron or less has been reported (for example, see Patent Document 2).
しかし、十分なサーモクロミック性と光透過性とを得るためには、上記特許文献に開示されているような技術では不十分であり、安定に粒子を作製することが必要である。 However, in order to obtain sufficient thermochromic properties and light transmittance, the technique disclosed in the above-mentioned patent document is insufficient, and it is necessary to produce particles stably.
本発明は、上記問題・状況に鑑みてなされたものであり、その解決課題は、サーモクロミック性及び光透過性に優れた酸化バナジウム含有粒子の製造方法及び酸化バナジウム含有粒子を提供することである。 The present invention has been made in view of the above problems and circumstances, and a solution to that problem is to provide a method for producing vanadium oxide-containing particles excellent in thermochromic properties and light transmittance, and vanadium oxide-containing particles. .
本発明者は、上記課題を解決すべく、上記問題の原因等について検討する過程において、酸化バナジウム含有粒子を製造する工程において、バナジウム化合物の初期濃度を特定範囲内とすることにより、サーモクロミック性及び光透過性に優れた酸化バナジウム含有粒子（二酸化バナジウム粒子を含む。）を提供できることを見出し、本発明に至った。 In order to solve the above-mentioned problems, the present inventor, in the process of studying the cause of the above-mentioned problems, in the step of producing vanadium oxide-containing particles, by making the initial concentration of the vanadium compound within a specific range, thermochromic properties In addition, the inventors have found that vanadium oxide-containing particles (including vanadium dioxide particles) excellent in light transmittance can be provided, and have reached the present invention.
すなわち、本発明に係る上記課題は、以下の手段により解決される。 That is, the said subject which concerns on this invention is solved by the following means.
１．サーモクロミック性を有する酸化バナジウム含有粒子の製造方法であって、
バナジウム化合物、還元剤及び水を準備する工程と、
前記バナジウム化合物、前記還元剤及び前記水を混合して、水熱反応により前記酸化バナジウム含有粒子を製造する工程と、
を有し、
前記酸化バナジウム含有粒子を製造する工程では、前記バナジウム化合物の初期濃度を５．０×１０−５〜５．０×１０−２ｍｏｌ／Ｌの範囲内とすることを特徴とする酸化バナジウム含有粒子の製造方法。
1. A method for producing vanadium oxide-containing particles having thermochromic properties,
Preparing a vanadium compound, a reducing agent and water;
Mixing the vanadium compound, the reducing agent and the water, and producing the vanadium oxide-containing particles by a hydrothermal reaction;
Have
In the step of producing the vanadium oxide-containing particles, the vanadium oxide-containing particles are characterized in that an initial concentration of the vanadium compound is in a range of 5.0 × 10 −5 to 5.0 × 10 −2 mol / L. Manufacturing method.
２．前記酸化バナジウム含有粒子を製造する工程では、前記バナジウム化合物の初期濃度を５．０×１０−４〜２．５×１０−２ｍｏｌ／Ｌの範囲内とすることを特徴とする第１項に記載の酸化バナジウム含有粒子の製造方法。 2. Item 1 is characterized in that, in the step of producing the vanadium oxide-containing particles, the initial concentration of the vanadium compound is in the range of 5.0 × 10 −4 to 2.5 × 10 −2 mol / L. The manufacturing method of vanadium oxide containing particle | grains of description.
３．前記酸化バナジウム含有粒子を製造する工程では、前記バナジウム化合物の初期濃度を５．０×１０−４〜２．５×１０−３ｍｏｌ／Ｌの範囲内とすることを特徴とする第２項に記載の酸化バナジウム含有粒子の製造方法。 3. Item 2 is characterized in that, in the step of manufacturing the vanadium oxide-containing particles, the initial concentration of the vanadium compound is in the range of 5.0 × 10 −4 to 2.5 × 10 −3 mol / L. The manufacturing method of vanadium oxide containing particle | grains of description.
４．前記還元剤量が、前記バナジウム化合物１．００ｍｏｌに対して、０．１０〜０．７０ｍｏｌの範囲内であることを特徴とする第１項から第３項までのいずれか一項に記載の酸化バナジウム含有粒子の製造方法。 4). The oxidation according to any one of Items 1 to 3, wherein the amount of the reducing agent is within a range of 0.10 to 0.70 mol with respect to 1.00 mol of the vanadium compound. A method for producing vanadium-containing particles.
５．前記バナジウム化合物が、五酸化二バナジウム、バナジン酸アンモニウム又は三塩化酸化バナジウムであることを特徴とする第１項から第４項までのいずれか一項に記載の酸化バナジウム含有粒子の製造方法。 5. The method for producing vanadium oxide-containing particles according to any one of items 1 to 4, wherein the vanadium compound is divanadium pentoxide, ammonium vanadate or vanadium trichloride oxide.
６．前記還元剤が、シュウ酸又はヒドラジン化合物であることを特徴とする第１項から第５項までのいずれか一項に記載の酸化バナジウム含有粒子の製造方法。 6). The method for producing vanadium oxide-containing particles according to any one of items 1 to 5, wherein the reducing agent is oxalic acid or a hydrazine compound.
７．前記酸化バナジウム含有粒子を製造する工程では、水熱反応を２３０〜３５０℃の範囲内で行い、反応終了後、３０分以内に１５０℃以下まで冷却することを特徴とする第１項から第６項までのいずれか一項に記載の酸化バナジウム含有粒子の製造方法。 7). In the step of producing the vanadium oxide-containing particles, a hydrothermal reaction is performed within a range of 230 to 350 ° C., and the reaction is cooled to 150 ° C. or less within 30 minutes after completion of the reaction. The manufacturing method of the vanadium oxide containing particle | grains as described in any one to the term.
８．第１項から第７項までのいずれか一項に記載の酸化バナジウム含有粒子の製造方法により製造された、サーモクロミック性を有する酸化バナジウム含有粒子であって、
粒径分布において、前記酸化バナジウム含有粒子の累積存在比率が８０％となる粒径が、１〜１５０ｎｍの範囲内であることを特徴とする酸化バナジウム含有粒子。
8). A vanadium oxide-containing particle having thermochromic properties, produced by the method for producing a vanadium oxide-containing particle according to any one of items 1 to 7,
A vanadium oxide-containing particle characterized in that, in a particle size distribution, a particle size at which a cumulative abundance ratio of the vanadium oxide-containing particle is 80% is in a range of 1 to 150 nm.
本発明の上記手段により、サーモクロミック性及び光透過性に優れた酸化バナジウム含有粒子の製造方法及び酸化バナジウム含有粒子を提供することができる。 By the above means of the present invention, a method for producing vanadium oxide-containing particles and vanadium oxide-containing particles having excellent thermochromic properties and light transmittance can be provided.
本発明の効果の発現機構・作用機構については明確になっていないが、以下のように推察している。 The expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.
本発明の酸化バナジウム含有粒子の製造方法は、バナジウム化合物の初期濃度を５．０×１０−５〜５．０×１０−２ｍｏｌ／Ｌの範囲内とすることを特徴とする。
これにより、水熱反応中に生成した二酸化バナジウム粒子同士が結着する頻度を低減させ、反応系中で二酸化バナジウム粒子生成時に生じる凝集や粗大粒子化を防ぐことができるものと考えられる。
The method for producing vanadium oxide-containing particles of the present invention is characterized in that the initial concentration of the vanadium compound is in the range of 5.0 × 10 −5 to 5.0 × 10 −2 mol / L.
Thereby, it is considered that the frequency at which the vanadium dioxide particles produced during the hydrothermal reaction are bound to each other can be reduced, and aggregation and coarsening that occur when the vanadium dioxide particles are produced in the reaction system can be prevented.
また、バナジウム化合物の初期濃度を５．０×１０−５ｍｏｌ／Ｌより小さくすると、反応が十分に進行せず、初期濃度を５．０×１０−２ｍｏｌ／Ｌより大きくすると、粒形が大きくなり、粒形分布も広くなってしまう。濃度が低すぎると収率の低下にも繋がるため、濃度は適正な範囲とする必要がある。 Further, when the initial concentration of the vanadium compound is smaller than 5.0 × 10 −5 mol / L, the reaction does not proceed sufficiently, and when the initial concentration is larger than 5.0 × 10 −2 mol / L, the particle shape is reduced. It becomes larger and the particle shape distribution becomes wider. If the concentration is too low, it leads to a decrease in yield, so the concentration needs to be in an appropriate range.
本発明の酸化バナジウム含有粒子の製造方法は、酸化バナジウム含有粒子を製造する工程において、バナジウム化合物の初期濃度を５．０×１０−５〜５．０×１０−２ｍｏｌ／Ｌの範囲内とすることを特徴とする。この特徴は、請求項１から請求項８までの請求項に係る発明に共通する技術的特徴である。 In the method for producing vanadium oxide-containing particles of the present invention, in the step of producing vanadium oxide-containing particles, the initial concentration of the vanadium compound is in the range of 5.0 × 10 −5 to 5.0 × 10 −2 mol / L. It is characterized by doing. This feature is a technical feature common to the inventions according to claims 1 to 8.
本発明の実施態様としては、より酸化バナジウム含有粒子の優れたサーモクロミック性と、当該酸化バナジウム含有粒子を添加したフィルムの可視光領域における光透過性とを得る観点から、酸化バナジウム含有粒子を製造する工程におけるバナジウム化合物の初期濃度を５．０×１０−４〜２．５×１０−２ｍｏｌ／Ｌの範囲内とすることが好ましく、５．０×１０−４〜２．５×１０−３ｍｏｌ／Ｌの範囲内とすることがより好ましい。 As an embodiment of the present invention, vanadium oxide-containing particles are produced from the viewpoint of obtaining better thermochromic properties of vanadium oxide-containing particles and light transmittance in a visible light region of a film to which the vanadium oxide-containing particles are added. preferably in the range of initial concentration of 5.0 × 10 -4 ~2.5 × 10 -2 mol / L of the vanadium compound in the process of, 5.0 × 10 -4 ~2.5 × 10 - More preferably, it is within the range of 3 mol / L.
また、水熱反応を適度に制御し、目的とする二酸化バナジウム粒子の純度を高くし、粒形のバラツキや粗大化を防止する観点から、還元剤量がバナジウム化合物１．００ｍｏｌに対して、０．１０〜０．７０ｍｏｌの範囲内であることが好ましい。 Further, from the viewpoint of appropriately controlling the hydrothermal reaction, increasing the purity of the intended vanadium dioxide particles, and preventing variation in particle shape and coarsening, the amount of the reducing agent is 0 with respect to 1.00 mol of the vanadium compound. It is preferable to be within the range of .10 to 0.70 mol.
また、反応性の観点から、バナジウム化合物が、五酸化二バナジウム、バナジン酸アンモニウム又は三塩化酸化バナジウムであることが好ましい。 From the viewpoint of reactivity, the vanadium compound is preferably divanadium pentoxide, ammonium vanadate or vanadium trichloride oxide.
また、還元性の観点から、還元剤が、シュウ酸又はヒドラジン化合物であることが好ましい。 From the viewpoint of reducing properties, the reducing agent is preferably oxalic acid or a hydrazine compound.
また、酸化バナジウム含有粒子を製造する工程では、水熱反応を２３０〜３５０℃の範囲内で行い、反応終了後、３０分以内に１５０℃以下まで冷却することが好ましい。冷却速度が遅い場合、一部溶解している二酸化バナジウム粒子が冷却され析出する過程において、系内で温度分布が生じ、粒子同士の凝集や粒子の粗大化の原因となってしまう。そこで、反応温度（２３０〜３５０℃）から１５０℃までの冷却時間を３０分以内とすることで、この粒子の凝集や粗大化を防ぐことができる。 In the step of producing the vanadium oxide-containing particles, it is preferable that the hydrothermal reaction is performed within a range of 230 to 350 ° C., and is cooled to 150 ° C. or less within 30 minutes after the completion of the reaction. When the cooling rate is slow, a temperature distribution is generated in the system in the process of cooling and precipitating partially dissolved vanadium dioxide particles, which causes aggregation of particles and coarsening of the particles. Therefore, by setting the cooling time from the reaction temperature (230 to 350 ° C.) to 150 ° C. within 30 minutes, aggregation and coarsening of the particles can be prevented.
また、本発明の酸化バナジウム含有粒子の製造方法により製造された、サーモクロミック性を有する酸化バナジウム含有粒子は、粒径分布において、酸化バナジウム含有粒子の累積存在比率が８０％となる粒径が、１〜１５０ｎｍの範囲内であることを特徴とする。 Further, the vanadium oxide-containing particles having thermochromic properties produced by the method for producing vanadium oxide-containing particles of the present invention have a particle size distribution such that the cumulative abundance ratio of vanadium oxide-containing particles is 80%. It is characterized by being in the range of 1 to 150 nm.
以下、本発明とその構成要素、及び本発明を実施するための形態・態様について詳細な説明をする。なお、本願において、数値範囲を表す「〜」は、その前後に記載される数値を下限値及び上限値として含む意味で使用している。 Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" showing a numerical range is used by the meaning containing the numerical value described before and behind that as a lower limit and an upper limit.
≪酸化バナジウム含有粒子の製造方法≫
本発明のサーモクロミック性を有する酸化バナジウム含有粒子の製造方法は、バナジウム化合物、還元剤及び水を準備する工程と、バナジウム化合物、還元剤及び水を混合して、水熱反応により酸化バナジウム含有粒子を製造する工程と、を有し、酸化バナジウム含有粒子を製造する工程では、バナジウム化合物の初期濃度を５．０×１０−５〜５．０×１０−２ｍｏｌ／Ｌの範囲内とすることを特徴とする。
なお、本発明において、酸化バナジウム含有粒子とは、少なくとも二酸化バナジウム粒子を含む粒子である。酸化バナジウム含有粒子は、該粒子中に二酸化バナジウム粒子以外の成分を含んでいてもよいし、二酸化バナジウム粒子のみから形成されていてもよい。
≪Method for producing vanadium oxide-containing particles≫
The method for producing thermochromic vanadium oxide-containing particles of the present invention includes a step of preparing a vanadium compound, a reducing agent and water, and a mixture of the vanadium compound, the reducing agent and water, and the vanadium oxide-containing particles by a hydrothermal reaction. In the step of manufacturing vanadium oxide-containing particles, the initial concentration of the vanadium compound is within the range of 5.0 × 10 −5 to 5.0 × 10 −2 mol / L. It is characterized by.
In the present invention, the vanadium oxide-containing particles are particles containing at least vanadium dioxide particles. The vanadium oxide-containing particles may contain components other than vanadium dioxide particles in the particles, or may be formed of vanadium dioxide particles alone.
＜水熱反応＞
本発明のサーモクロミック性及び光透過性を有する酸化バナジウム含有粒子の製造方法について説明する。
本発明では、バナジウム化合物を水熱反応下で還元することで、ルチル型二酸化バナジウム粒子を含む酸化バナジウム含有粒子を合成する。
<Hydrothermal reaction>
The manufacturing method of the vanadium oxide containing particle | grains which has the thermochromic property and light transmittance of this invention is demonstrated.
In the present invention, vanadium oxide-containing particles containing rutile vanadium dioxide particles are synthesized by reducing the vanadium compound under a hydrothermal reaction.
より詳しくは、バナジウム化合物及び還元剤を水に混合し、オートクレーブ中、好ましくは２３０〜３５０℃の範囲内で水熱合成を行う。このとき、過酸化水素を混合してもよい。
バナジウム化合物の初期濃度（水熱反応開始時点での濃度）は、５．０×１０−５〜５．０×１０−２ｍｏｌ／Ｌの範囲内であり、好ましくは５．０×１０−４〜２．５×１０−２ｍｏｌ／Ｌの範囲内、より好ましくは５．０×１０−４〜２．５×１０−３ｍｏｌ／Ｌの範囲内である。
還元剤量は、バナジウム化合物１．００ｍｏｌに対して、０．１０〜１．００ｍｏｌの範囲内が好ましく、特に０．１０〜０．７０ｍｏｌの範囲内であることがより好ましい。
反応時間は、温度によって異なるため、反応の進行具合を確認して決める。
More specifically, a vanadium compound and a reducing agent are mixed with water, and hydrothermal synthesis is performed in an autoclave, preferably in the range of 230 to 350 ° C. At this time, hydrogen peroxide may be mixed.
The initial concentration of vanadium compound (concentration at the start of hydrothermal reaction) is in the range of 5.0 × 10 −5 to 5.0 × 10 −2 mol / L, preferably 5.0 × 10 −4. It is in the range of ˜2.5 × 10 −2 mol / L, more preferably in the range of 5.0 × 10 −4 to 2.5 × 10 −3 mol / L.
The amount of the reducing agent is preferably in the range of 0.10 to 1.00 mol, and more preferably in the range of 0.10 to 0.70 mol, with respect to 1.00 mol of the vanadium compound.
Since the reaction time varies depending on the temperature, it is determined by confirming the progress of the reaction.
反応終了後、速やかに１５０℃以下まで冷却することが好ましい。より好ましくは、３０分以内に１５０℃以下まで冷却する。
また、限外濾過を用いて溶媒の置換を行い、洗浄を行ってもよい。
After completion of the reaction, it is preferable to quickly cool to 150 ° C. or less. More preferably, it cools to 150 degrees C or less within 30 minutes.
Further, the solvent may be replaced by using ultrafiltration to perform washing.
酸化バナジウム含有粒子は、所定の溶媒（分散媒）中に分散させて、分散液としてもよい。分散媒としては、特に限定されるものではなく、公知のものを使用することができる。 The vanadium oxide-containing particles may be dispersed in a predetermined solvent (dispersion medium) to form a dispersion. The dispersion medium is not particularly limited, and a known medium can be used.
（限外濾過）
限外濾過としては、例えば、Ｓａｒｔｏｒｉｕｓ ｓｔｅｄｉｍ社製、ビバフロー５０（有効濾過面積５０ｃｍ２、分画分子量５０００）を用いて、流速３００ｍＬ／ｍｉｎ、液圧１ｂａｒ（０．１ＭＰａ）、常温（２０〜３０℃）で濾過を行うことができる。
(Ultrafiltration)
As ultrafiltration, for example, using Vivaflow 50 (effective filtration area 50 cm 2 , molecular weight cut-off 5000) manufactured by Sartorius steady, flow rate 300 mL / min, liquid pressure 1 bar (0.1 MPa), normal temperature (20-30) Filtration).
≪酸化バナジウム含有粒子≫
本発明の酸化バナジウム含有粒子は、少なくともルチル型二酸化バナジウム粒子を含んで構成され、これにより、サーモクロミック性と光透過性とを発現することができる。
酸化バナジウム含有粒子を添加したフィルムの光透過率は、高いほど好ましいが、７０％以上であることが好ましい。
また、酸化バナジウム含有粒子が有するサーモクロミック性としては、温度変化によって光透過率や光反射率等の光学特性が可逆的に変化すれば特に限定されるものではない。例えば、２５℃／５０％ＲＨ及び８５℃／５０％ＲＨにおける光透過率の差が３０％以上であることが好ましい。
酸化バナジウム含有粒子を添加したフィルムの光透過率は、例えば、分光光度計Ｖ−６７０（日本分光株式会社製）を用いて、波長２０００ｎｍにおける光透過率として測定することができる。
≪Vanadium oxide-containing particles≫
The vanadium oxide-containing particles of the present invention are configured to include at least rutile-type vanadium dioxide particles, and thereby can exhibit thermochromic properties and light transmittance.
The light transmittance of the film to which the vanadium oxide-containing particles are added is preferably as high as possible, but is preferably 70% or more.
Further, the thermochromic property of the vanadium oxide-containing particles is not particularly limited as long as optical characteristics such as light transmittance and light reflectance change reversibly due to temperature change. For example, the difference in light transmittance at 25 ° C./50% RH and 85 ° C./50% RH is preferably 30% or more.
The light transmittance of the film to which the vanadium oxide-containing particles are added can be measured as the light transmittance at a wavelength of 2000 nm using, for example, a spectrophotometer V-670 (manufactured by JASCO Corporation).
また、本発明の酸化バナジウム含有粒子は、粒径分布において、酸化バナジウム含有粒子の累積存在比率が８０％となる粒径が、１〜１５０ｎｍの範囲内であることを特徴とする。本発明において、存在比率の基準は、個数基準（個数分布）とする。
以上のように、二酸化バナジウム粒子を含む本発明のサーモクロミック性を有する酸化バナジウム含有粒子は、粒径が小さく、粒径分布も狭いことから、優れたサーモクロミック性と、酸化バナジウム含有粒子を添加したフィルムの可視光領域における光透過性を発現可能となる。
なお、本発明において、酸化バナジウム含有粒子の粒径は、レーザー回折式粒度分布計で測定し、例えば、島津製作所製のレーザー回折式粒度分布測定装置等を用いることができる。測定対象物（サンプル）の適正な濃度範囲は、各装置により異なるため、適宜濃縮、希釈して用いる。
The vanadium oxide-containing particles of the present invention are characterized in that, in the particle size distribution, the particle size at which the cumulative abundance ratio of vanadium oxide-containing particles is 80% is in the range of 1 to 150 nm. In the present invention, the existence ratio criterion is the number criterion (number distribution).
As described above, the vanadium oxide-containing particles having the thermochromic properties of the present invention including vanadium dioxide particles have a small particle size and a narrow particle size distribution, so that excellent thermochromic properties and vanadium oxide-containing particles are added. The light transmittance in the visible light region of the obtained film can be expressed.
In the present invention, the particle size of the vanadium oxide-containing particles is measured with a laser diffraction particle size distribution meter, and for example, a laser diffraction particle size distribution measuring device manufactured by Shimadzu Corporation can be used. Since the appropriate concentration range of the measurement object (sample) varies depending on each device, it is appropriately concentrated and diluted for use.
≪バナジウム化合物≫
本発明に係るバナジウム化合物としては、特に限定されないが、五酸化二バナジウム（Ｖ２Ｏ５）、バナジン酸アンモニウム又は三塩化酸化バナジウムであることが好ましい。
≪Vanadium compounds≫
The vanadium compound according to the present invention is not particularly limited, but is preferably divanadium pentoxide (V 2 O 5 ), ammonium vanadate or vanadium trichloride oxide.
≪還元剤≫
本発明に係る還元剤としては、特に限定されないが、シュウ酸又はヒドラジンであることが好ましい。
≪Reducing agent≫
The reducing agent according to the present invention is not particularly limited, but is preferably oxalic acid or hydrazine.
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例において「％」の表示を用いるが、特に断りがない限り「質量％」を表す。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.
≪酸化バナジウム含有粒子分散液の作製≫
（１）サンプル１０１の作製
３５質量％の過酸化水素水（和光純薬社製）２ｍＬと純水１５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．５５ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を２．４ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は１５×１０−２ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は１．００ｍｏｌである。
≪Preparation of vanadium oxide-containing particle dispersion≫
(1) Preparation of Sample 101 To an aqueous solution obtained by mixing 2 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , special grade, Japanese After adding 0.55 g (light pure drug) and stirring at 30 ° C. for 4 hours, a 1.25 mol / L aqueous solution of hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, Ltd., special grade) was added. 4 mL was slowly added dropwise.
The concentration of the vanadium compound at this time is 15 × 10 −2 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 1.00 mol.
調製した混合液を、高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、反応系の温度が１５０℃まで下がるには３時間を費やした。
The prepared liquid mixture is put into a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: manufactured by Sanai Kagaku), heated at 100 ° C. for 8 hours, and then 270 ° C. -The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, it took 3 hours for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１０１とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（２）サンプル１０２の作製
３５質量％の過酸化水素水（和光純薬社製）２ｍＬと純水１５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．１６ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．７３ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は５．０×１０−２ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は１．００ｍｏｌである。
(2) Preparation of Sample 102 To an aqueous solution obtained by mixing 2 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , special grade, Japanese After adding 0.16 g (light pure drug) and stirring at 30 ° C. for 4 hours, a 1.25 mol / L aqueous solution of hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, Ltd., special grade) 73 mL was slowly added dropwise.
At this time, the concentration of the vanadium compound is 5.0 × 10 −2 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 1.00 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、反応系の温度が１５０℃まで下がるには３時間を費やした。
The adjusted liquid mixture is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, it took 3 hours for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１０２とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（３）サンプル１０３の作製
３５質量％の過酸化水素水（和光純薬社製）５ｍＬと純水４５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．０００５ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．００２３ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は５．０×１０−５ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は１．００ｍｏｌである。
(3) Preparation of Sample 103 To an aqueous solution obtained by mixing 5 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 45 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , special grade, Japanese After adding 0.0005 g (light pure drug) and stirring at 30 ° C. for 4 hours, a 1.25 mol / L aqueous solution of hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, Ltd., special grade) 0023 mL was slowly added dropwise.
At this time, the concentration of the vanadium compound is 5.0 × 10 −5 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 1.00 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ １００ｍＬセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−１００：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、反応系の温度が１５０℃まで下がるには３時間を費やした。
The adjusted mixed solution is put into a 100 mL set of high pressure reaction decomposition vessel stationary HU (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-100: manufactured by Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, it took 3 hours for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１０３とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（４）サンプル１０４の作製
３５質量％の過酸化水素水（和光純薬社製）５ｍＬと純水４５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．０００４ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．００１８ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は４．０×１０−５ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は１．００ｍｏｌである。
(4) Preparation of Sample 104 To an aqueous solution obtained by mixing 5 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 45 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , special grade, Japanese After adding 0.0004 g (light pure drug) and stirring at 30 ° C. for 4 hours, a 1.25 mol / L aqueous solution of hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, special grade) 0018 mL was slowly added dropwise.
The concentration of the vanadium compound at this time is 4.0 × 10 −5 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 1.00 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ １００ｍＬセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−１００：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、反応系の温度が１５０℃まで下がるには３時間を費やした。
The adjusted mixed solution is put into a 100 mL set of high pressure reaction decomposition vessel stationary HU (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-100: manufactured by Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, it took 3 hours for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１０４とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（５）サンプル１０５の作製
３５質量％の過酸化水素水（和光純薬社製）２ｍＬと純水１５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．０７９ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．３３ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は２．５×１０−２ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は１．００ｍｏｌである。
(5) Preparation of Sample 105 To an aqueous solution obtained by mixing 2 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , special grade, Japanese After adding 0.079 g (light pure drug) and stirring at 30 ° C. for 4 hours, a 1.25 mol / L aqueous solution of hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, Ltd., special grade) 33 mL was slowly added dropwise.
At this time, the concentration of the vanadium compound is 2.5 × 10 −2 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 1.00 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、反応系の温度が１５０℃まで下がるには３時間を費やした。
The adjusted liquid mixture is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, it took 3 hours for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１０５とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（６）サンプル１０６の作製
３５質量％の過酸化水素水（和光純薬社製）２ｍＬと純水１５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．００７８ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．０３４ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は２．５×１０−３ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は１．００ｍｏｌである。
(6) Preparation of Sample 106 To an aqueous solution obtained by mixing 2 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , special grade, Japanese After adding 0.0078 g (light pure drug) and stirring at 30 ° C. for 4 hours, a 1.25 mol / L aqueous solution of hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, Ltd., special grade) 034 mL was slowly added dropwise.
At this time, the concentration of the vanadium compound is 2.5 × 10 −3 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 1.00 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、反応系の温度が１５０℃まで下がるには３時間を費やした。
The adjusted liquid mixture is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, it took 3 hours for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１０６とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（７）サンプル１０７の作製
３５質量％の過酸化水素水（和光純薬社製）２.３５ｍＬと純水１７．６５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．００１８ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．００８ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は５．０×１０−４ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は１．００ｍｏｌである。
(7) Preparation of Sample 107 To an aqueous solution obtained by mixing 2.35 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 17.65 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , Special grade, Wako Pure Chemicals) 0.0018 g was added and stirred at 30 ° C. for 4 hours, followed by 1.25 mol / L of hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, special grade). 0.008 mL of the aqueous solution was slowly added dropwise.
At this time, the concentration of the vanadium compound is 5.0 × 10 −4 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 1.00 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、反応系の温度が１５０℃まで下がるには３時間を費やした。
The adjusted liquid mixture is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, it took 3 hours for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１０７とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（８）サンプル１０８の作製
３５質量％の過酸化水素水（和光純薬社製）２.３５ｍＬと純水１７．６５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．００９１ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．０２ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は２．５×１０−３ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は０．５０ｍｏｌである。
(8) Preparation of Sample 108 To an aqueous solution obtained by mixing 2.35 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 17.65 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , Special grade, Wako Pure Chemical Industries, Ltd.) 0.0091 g was added and stirred at 30 ° C. for 4 hours, then hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, special grade) was 1.25 mol / L. 0.02 mL of the aqueous solution was slowly added dropwise.
The concentration of the vanadium compound at this time is 2.5 × 10 −3 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 0.50 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、反応系の温度が１５０℃まで下がるには３時間を費やした。
The adjusted liquid mixture is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, it took 3 hours for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１０８とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（９）サンプル１０９の作製
３５質量％の過酸化水素水（和光純薬社製）２.３５ｍＬと純水１７．６５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．００９１ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．０２８ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は２．５×１０−３ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は０．７０ｍｏｌである。
(9) Preparation of Sample 109 To an aqueous solution obtained by mixing 2.35 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 17.65 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , Special grade, Wako Pure Chemical Industries, Ltd.) 0.0091 g was added and stirred at 30 ° C. for 4 hours, then hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, special grade) was 1.25 mol / L. 0.028 mL of the aqueous solution was slowly added dropwise.
At this time, the concentration of the vanadium compound is 2.5 × 10 −3 mol / L, and the amount of the reducing agent relative to 1.00 mol of the vanadium compound is 0.70 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、反応系の温度が１５０℃まで下がるには３時間を費やした。
The adjusted liquid mixture is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, it took 3 hours for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１０９とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（１０）サンプル１１０の作製
３５質量％の過酸化水素水（和光純薬社製）２.３５ｍＬと純水１７．６５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．００９１ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．００４ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は２．５×１０−３ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は０．１０ｍｏｌである。
(10) Preparation of Sample 110 To an aqueous solution obtained by mixing 2.35 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 17.65 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , Special grade, Wako Pure Chemical Industries, Ltd.) 0.0091 g was added and stirred at 30 ° C. for 4 hours, then hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, special grade) was 1.25 mol / L. 0.004 mL of the aqueous solution was slowly added dropwise.
At this time, the concentration of the vanadium compound is 2.5 × 10 −3 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 0.10 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、反応系の温度が１５０℃まで下がるには３時間を費やした。
The adjusted liquid mixture is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, it took 3 hours for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１１０とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（１１）サンプル１１１の作製
３５質量％の過酸化水素水（和光純薬社製）２.３５ｍＬと純水１７．６５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．００９１ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．００３ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は２．５×１０−３ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は０．０８ｍｏｌである。
(11) Preparation of Sample 111 Into an aqueous solution obtained by mixing 2.35 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 17.65 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , Special grade, Wako Pure Chemical Industries, Ltd.) 0.0091 g was added and stirred at 30 ° C. for 4 hours, then hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, special grade) was 1.25 mol / L. 0.003 mL of the aqueous solution was slowly added dropwise.
At this time, the concentration of the vanadium compound is 2.5 × 10 −3 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 0.08 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、反応系の温度が１５０℃まで下がるには３時間を費やした。
The adjusted liquid mixture is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, it took 3 hours for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１１１とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（１２）サンプル１１２の作製
３５質量％の過酸化水素水（和光純薬社製）２.３５ｍＬと純水１７．６５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．００９１ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．０２ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は２．５×１０−３ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は０．５０ｍｏｌである。
(12) Preparation of Sample 112 To an aqueous solution obtained by mixing 2.35 mL of 35% by mass of hydrogen peroxide water (manufactured by Wako Pure Chemical Industries, Ltd.) and 17.65 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , Special grade, Wako Pure Chemical Industries, Ltd.) 0.0091 g was added and stirred at 30 ° C. for 4 hours, then hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, special grade) was 1.25 mol / L. 0.02 mL of the aqueous solution was slowly added dropwise.
The concentration of the vanadium compound at this time is 2.5 × 10 −3 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 0.50 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、素早く反応容器を常温（２５℃）下にして冷却した。反応系の温度が１５０℃まで下がるには２５分間を費やした。
The adjusted liquid mixture is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, the reaction vessel was quickly cooled to room temperature (25 ° C.). It took 25 minutes for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１１２とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（１３）サンプル１１３の作製
純水２０．０ｍＬに、バナジン酸アンモニウム（ＮＨ４ＶＯ３、特級、和光純薬）０．００５８５ｇを加え、３０℃で４時間撹拌後、ヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．０２ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は２．５×１０−３ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は０．５０ｍｏｌである。
(13) Preparation of Sample 113 To 50.0 mL of pure water, 0.00585 g of ammonium vanadate (NH 4 VO 3 , special grade, Wako Pure Chemical Industries) was added, stirred at 30 ° C. for 4 hours, and then hydrazine monohydrate (N 0.02 mL of a 1.25 mol / L aqueous solution of 2 H 4 .H 2 O (manufactured by Wako Pure Chemical Industries, Ltd., special grade) was slowly added dropwise.
The concentration of the vanadium compound at this time is 2.5 × 10 −3 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 0.50 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、素早く反応容器を常温（２５℃）下にして冷却した。反応系の温度が１５０℃まで下がるには２５分間を費やした。
The adjusted liquid mixture is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, the reaction vessel was quickly cooled to room temperature (25 ° C.). It took 25 minutes for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１１３とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
（１４）サンプル１１４の作製
３５質量％の過酸化水素水（和光純薬社製）２.３５ｍＬと純水１７．６５ｍＬとを混合した水溶液に、五酸化二バナジウム（Ｖ）（Ｖ２Ｏ５、特級、和光純薬）０．００９１ｇを加え、３０℃で４時間撹拌後、シュウ酸二水和物（Ｈ２Ｃ２Ｏ４・２Ｈ２Ｏ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を０．０２ｍＬゆっくり滴下した。
このときのバナジウム化合物の濃度は２．５×１０−３ｍｏｌ／Ｌ、バナジウム化合物１．００ｍｏｌに対する還元剤の量は０．５０ｍｏｌである。
(14) Preparation of Sample 114 To an aqueous solution obtained by mixing 2.35 mL of 35% by mass of hydrogen peroxide water (manufactured by Wako Pure Chemical Industries, Ltd.) and 17.65 mL of pure water, divanadium pentoxide (V) (V 2 O 5 , special grade, added Wako pure Chemical) 0.0091G, 1 after 4 hours at 30 ° C., oxalic acid dihydrate (H 2 C 2 O 4 · 2H 2 O, manufactured by Wako pure Chemical Industries, Ltd., special grade). 0.02 mL of 25 mol / L aqueous solution was slowly added dropwise.
The concentration of the vanadium compound at this time is 2.5 × 10 −3 mol / L, and the amount of the reducing agent with respect to 1.00 mol of the vanadium compound is 0.50 mol.
調整した混合液を高圧用反応分解容器 静置型ＨＵ ５０ｍｌセット（耐圧ステンレス製外筒、ＰＴＦＥ製試料容器 ＨＵＴｃ−５０：三愛科学社製）に入れて、１００℃で８時間加熱後、２７０℃・４８時間の水熱反応を行った。
反応停止後に、素早く反応容器を常温（２５℃）下にして冷却した。反応系の温度が１５０℃まで下がるには２５分間を費やした。
The adjusted liquid mixture is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: Sanai Kagaku Co., Ltd.), heated at 100 ° C. for 8 hours, 270 ° C. The hydrothermal reaction was performed for 48 hours.
After stopping the reaction, the reaction vessel was quickly cooled to room temperature (25 ° C.). It took 25 minutes for the temperature of the reaction system to drop to 150 ° C.
得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム粒子を含む酸化バナジウム含有粒子の水分散液を作製し、サンプル１１４とした。 The obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium oxide-containing particles containing vanadium dioxide particles.
≪サンプルの評価≫
（１）粒径分布測定
作製した各サンプルについて、レーザー回折式粒度分布計を用いて、粒形分布を測定した。
具体的には、作製した各サンプルについて、酸化バナジウム含有粒子の濃度が１質量％となるように水と混合し、超音波で１５分間分散してサンプルを作製し、島津製作所製のレーザー回折式粒度分布測定装置を用いて測定した。
測定値の指標は、累積存在比率が８０％となる粒径（ｎｍ）を用い、下記評価基準に従って評価した。
評価結果を表１に示す。
≪Sample evaluation≫
(1) Particle size distribution measurement About each produced sample, the particle shape distribution was measured using the laser diffraction type particle size distribution meter.
Specifically, each sample prepared was mixed with water so that the concentration of the vanadium oxide-containing particles was 1% by mass, and dispersed with ultrasound for 15 minutes to prepare a sample. It measured using the particle size distribution measuring apparatus.
The measured value index was evaluated according to the following evaluation criteria using a particle size (nm) with a cumulative abundance ratio of 80%.
The evaluation results are shown in Table 1.
◎：５０ｎｍ未満
○：５０ｎｍ以上１００ｎｍ未満
△：１００ｎｍ以上１５０ｎｍ未満
×：１５０ｎｍ以上
◎: Less than 50 nm ○: 50 nm or more and less than 100 nm Δ: 100 nm or more and less than 150 nm ×: 150 nm or more
（２）ヘイズ測定
作製した各サンプルをポリビニルアルコール中に１質量％となるように混合し、厚さ２０μｍの測定用フィルムを作製した。作製した各測定用フィルムについて、日本電色工業株式会社製 ヘーズメーター ＮＤＨ７０００を用いて、ヘイズ値（％）の測定を行い、下記評価基準に従って評価した。
評価結果を表１に示す。
(2) Haze measurement Each of the prepared samples was mixed in polyvinyl alcohol so as to be 1% by mass to prepare a measurement film having a thickness of 20 μm. About each produced film for a measurement, haze value (%) was measured using Nippon Denshoku Industries Co., Ltd. haze meter NDH7000, and it evaluated according to the following evaluation criteria.
The evaluation results are shown in Table 1.
◎：５％未満
○：５％以上１０％未満
△：１０％以上１５％未満
×：１５％以上
◎: Less than 5% ○: 5% or more and less than 10% △: 10% or more and less than 15% ×: 15% or more
（３）サーモクロミック特性の評価
作製した各サンプルをポリビニルアルコール中に１質量％となるように混合し、厚さ２０μｍの測定用フィルムを作製した。
各測定用フィルムを用いて、２５℃／５０％ＲＨ、８５℃／５０％ＲＨにおける波長２０００ｎｍでのそれぞれの光透過率を測定し、算出される透過率差（ΔＴ（％））を下記評価基準に従って評価した。
測定は、分光光度計Ｖ−６７０（日本分光株式会社製）に温調ユニット（日本分光株式会社製）を取り付けて行った。
評価結果を表１に示す。
(3) Evaluation of thermochromic characteristics Each of the prepared samples was mixed in polyvinyl alcohol so as to be 1% by mass, and a film for measurement having a thickness of 20 μm was prepared.
Using each measurement film, each light transmittance at a wavelength of 2000 nm at 25 ° C./50% RH and 85 ° C./50% RH was measured, and the calculated transmittance difference (ΔT (%)) was evaluated as follows. Evaluation was made according to criteria.
The measurement was performed by attaching a temperature control unit (manufactured by JASCO Corporation) to a spectrophotometer V-670 (manufactured by JASCO Corporation).
The evaluation results are shown in Table 1.
◎：２０％以上
○：１０％以上２０％未満
△：５％以上１０％未満
×：５％未満
◎: 20% or more ○: 10% or more and less than 20% △: 5% or more and less than 10% ×: Less than 5%
（４）まとめ
表１から明らかなように、本発明のサンプルは、比較例のサンプルと比較して、サーモクロミック性及び光透過性に優れていることがわかる。
以上から、バナジウム化合物、還元剤及び水を準備する工程と、バナジウム化合物、還元剤及び水を混合して、水熱反応により酸化バナジウム含有粒子を製造する工程と、を有し、酸化バナジウム含有粒子を製造する工程では、バナジウム化合物の初期濃度を５．０×１０−５〜５．０×１０−２ｍｏｌ／Ｌの範囲内とする酸化バナジウム含有粒子の製造方法が、サーモクロミック性及び光透過性に優れた酸化バナジウム含有粒子の製造方法として有用であることが確認できた。
(4) Summary As is apparent from Table 1, it can be seen that the sample of the present invention is superior in thermochromic properties and light transmittance as compared with the sample of the comparative example.
From the above, the step of preparing the vanadium compound, the reducing agent and water, and the step of mixing the vanadium compound, the reducing agent and water to produce the vanadium oxide-containing particles by a hydrothermal reaction, the vanadium oxide-containing particles In the step of producing a vanadium oxide-containing particle having an initial concentration of the vanadium compound in the range of 5.0 × 10 −5 to 5.0 × 10 −2 mol / L, thermochromic properties and light transmission It was confirmed that it is useful as a method for producing vanadium oxide-containing particles having excellent properties.
Claims (8)
バナジウム化合物、還元剤及び水を準備する工程と、
前記バナジウム化合物、前記還元剤及び前記水を混合して、水熱反応により前記酸化バナジウム含有粒子を製造する工程と、
を有し、
前記酸化バナジウム含有粒子を製造する工程では、前記バナジウム化合物の初期濃度を５．０×１０−５〜５．０×１０−２ｍｏｌ／Ｌの範囲内とすることを特徴とする酸化バナジウム含有粒子の製造方法。 A method for producing vanadium oxide-containing particles having thermochromic properties,
Preparing a vanadium compound, a reducing agent and water;
Mixing the vanadium compound, the reducing agent and the water, and producing the vanadium oxide-containing particles by a hydrothermal reaction;
Have
In the step of producing the vanadium oxide-containing particles, the vanadium oxide-containing particles are characterized in that an initial concentration of the vanadium compound is in a range of 5.0 × 10 −5 to 5.0 × 10 −2 mol / L. Manufacturing method.
粒径分布において、前記酸化バナジウム含有粒子の累積存在比率が８０％となる粒径が、１〜１５０ｎｍの範囲内であることを特徴とする酸化バナジウム含有粒子。 A vanadium oxide-containing particle having thermochromic properties, produced by the method for producing a vanadium oxide-containing particle according to any one of claims 1 to 7,
A vanadium oxide-containing particle characterized in that, in a particle size distribution, a particle size at which a cumulative abundance ratio of the vanadium oxide-containing particle is 80% is in a range of 1 to 150 nm.
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