JP7044072B2 - Production method of vanadium dioxide-containing particles, thermochromic film and vanadium dioxide-containing particles - Google Patents
Production method of vanadium dioxide-containing particles, thermochromic film and vanadium dioxide-containing particles Download PDFInfo
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- JP7044072B2 JP7044072B2 JP2018554848A JP2018554848A JP7044072B2 JP 7044072 B2 JP7044072 B2 JP 7044072B2 JP 2018554848 A JP2018554848 A JP 2018554848A JP 2018554848 A JP2018554848 A JP 2018554848A JP 7044072 B2 JP7044072 B2 JP 7044072B2
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- vanadium
- vanadium dioxide
- containing particles
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- 239000002245 particle Substances 0.000 title claims description 115
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims description 104
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims description 102
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000007788 liquid Substances 0.000 claims description 62
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 51
- 229910052720 vanadium Inorganic materials 0.000 claims description 50
- 230000008859 change Effects 0.000 claims description 42
- 238000002834 transmittance Methods 0.000 claims description 38
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- 238000006243 chemical reaction Methods 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 33
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 32
- 239000011777 magnesium Substances 0.000 claims description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 20
- 239000011733 molybdenum Substances 0.000 claims description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
- 239000010937 tungsten Substances 0.000 claims description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 19
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- 230000035484 reaction time Effects 0.000 claims description 5
- PSDQQCXQSWHCRN-UHFFFAOYSA-N vanadium(4+) Chemical compound [V+4] PSDQQCXQSWHCRN-UHFFFAOYSA-N 0.000 claims description 4
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- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
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Description
本発明は、二酸化バナジウム含有粒子、サーモクロミックフィルム及び二酸化バナジウム含有粒子の製造方法に関し、より詳しくは、可視光領域において温度変化により光透過率を変化させるとともに、赤外光領域において温度変化による光透過率の変化幅をより増加させる二酸化バナジウム含有粒子、サーモクロミックフィルム及び二酸化バナジウム含有粒子の製造方法に関する。 The present invention relates to a method for producing vanadium dioxide-containing particles, a thermochromic film, and vanadium dioxide-containing particles. The present invention relates to a method for producing vanadium dioxide-containing particles, a thermochromic film, and vanadium dioxide-containing particles that further increase the change width of the transmittance.
例えば、住宅やビル等の建物、車両などの移動体等では、内部（例えば、室内、車両内。）と外部環境との間で大きな熱交換が生じる箇所（例えば、窓ガラス）において、省エネルギー性と快適性とを両立するために、熱の遮断又は透過を制御可能なサーモクロミック性を有する材料（以下、「サーモクロミック材料」ともいう。）の適用が期待されている。 For example, in a building such as a house or a building, a moving body such as a vehicle, energy saving is achieved in a place where a large heat exchange occurs between the inside (for example, indoors, inside the vehicle) and the external environment (for example, window glass). In order to achieve both comfort and comfort, the application of a thermochromic material (hereinafter, also referred to as "thermochromic material") capable of controlling heat blocking or transmission is expected.
ここで、「サーモクロミック材料」とは、透明状態／反射状態等の光学的な性質が、温度により可逆的に変化する材料である。例えば、温度が高い場合は反射状態となり、温度が低い場合は透明状態となる材料である。このようなサーモクロミック材料を、例えば、建物の窓ガラスに適用した場合には、夏には太陽光を反射させて熱を遮断でき、冬には太陽光を透過させて熱を利用できるため、省エネルギー性と快適性とを両立することができる。 Here, the "thermochromic material" is a material whose optical properties such as transparent state / reflective state change reversibly with temperature. For example, it is a material that becomes a reflective state when the temperature is high and becomes a transparent state when the temperature is low. When such a thermochromic material is applied to, for example, a window glass of a building, it can reflect sunlight to block heat in summer and transmit sunlight to utilize heat in winter. It is possible to achieve both energy saving and comfort.
現在、最も着目されているサーモクロミック材料の一つに、二酸化バナジウム（ＶＯ２）粒子がある。二酸化バナジウム粒子は、室温付近での相転移の際に、サーモクロミック性を示すことが知られている。したがって、この性質を利用することにより、環境温度に依存するサーモクロミック性を得ることができる。Currently, one of the thermochromic materials that has received the most attention is vanadium dioxide (VO 2 ) particles. Vanadium dioxide particles are known to exhibit thermochromic properties during a phase transition near room temperature. Therefore, by utilizing this property, it is possible to obtain thermochromic properties that depend on the environmental temperature.
ここで、二酸化バナジウムには、Ａ相、Ｂ相、Ｃ相及びＲ相など、いくつかの結晶相の多形が存在するが、前述のようなサーモクロミック特性を示す結晶構造は、ルチル型の結晶相（以下、「Ｒ相」という。）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、粒子中にサーモクロミック性を示さない金属や、二酸化バナジウムのＭ相以外の結晶相が存在しないことが望ましい。また、良好な光学特性（低ヘイズ）を得るためには、二酸化バナジウム粒子の粒子径ができるだけ均一で、かつ小さく（１００ｎｍ以下）、二酸化バナジウム粒子同士が凝集していないこと、粒子が等方的な形状を有していることが望ましい。このような粒子を作製する技術として、水熱反応を用いた合成方法が報告されている。Here, vanadium dioxide has polymorphs of several crystal phases such as A phase, B phase, C phase and R phase, but the crystal structure exhibiting the thermochromic characteristics as described above is of the rutyl type. It is limited to the crystalline phase (hereinafter referred to as "R phase"). This R phase is also called an M phase because it has a monoclinic structure below the transition temperature.
In order to exhibit substantially excellent thermochromic properties in such vanadium dioxide particles, it is desirable that the particles do not contain a metal that does not exhibit thermochromic properties or a crystal phase other than the M phase of vanadium dioxide. .. Further, in order to obtain good optical characteristics (low haze), the particle size of the vanadium dioxide particles is as uniform and small as possible (100 nm or less), the vanadium dioxide particles do not aggregate with each other, and the particles are isotropic. It is desirable to have a unique shape. As a technique for producing such particles, a synthesis method using a hydrothermal reaction has been reported.
例えば、特許文献１には、五酸化二バナジウム（Ｖ２Ｏ５）等を原料として、ヒドラジン（Ｎ２Ｈ４）又はその水和物（Ｎ２Ｈ４・ｎＨ２Ｏ）と水とを含み、二酸化チタン（ＴｉＯ２）粒子を実質的に含まない溶液を水熱反応させることにより得られる二酸化バナジウム（ＶＯ２）の単結晶微粒子が開示されている。
しかし、図９（実施例３）で示されているように、当該二酸化バナジウム粒子は、温度を上げていったときの光透過率変化が約６００ｎｍよりも長波長側（主に、赤外光領域）でのみ起こっており、サーモクロミック材料として適用しても効果を十分に発揮できず、また、サーモクロミック現象を視覚的に知覚することも難しい。For example, Patent Document 1 contains hydrazine (N 2 H 4 ) or a hydrate thereof (N 2 H 4 · n H 2 O) and water using divanadium pentoxide (V 2 O 5 ) or the like as a raw material. , Disclosed are monocrystalline fine particles of vanadium dioxide (VO 2 ) obtained by hydrothermally reacting a solution substantially free of titanium dioxide (TiO 2 ) particles.
However, as shown in FIG. 9 (Example 3), the vanadium dioxide particles have a light transmittance change on the longer wavelength side (mainly infrared light) than about 600 nm when the temperature is raised. It occurs only in the area), and even if it is applied as a thermochromic material, it cannot fully exert its effect, and it is also difficult to visually perceive the thermochromic phenomenon.
また、特許文献２には、マグネシウム又はアルミニウムがドープされ、その化学組成がＶ１－ｘＭｘＯ２（Ｍ：Ｍｇ又はＡｌ）である二酸化バナジウム粉末が開示されている。
しかし、上記特許文献１同様に、図８（実施例１０）で示されているように、当該二酸化バナジウム粉末は、光透過率変化が約６００ｎｍよりも長波長側（主に、赤外光領域）でのみ起こっており、サーモクロミック材料として適用しても効果を十分に発揮できず、また、サーモクロミック現象を視覚的に知覚することも難しい。Further, Patent Document 2 discloses a vanadium dioxide powder in which magnesium or aluminum is doped and the chemical composition thereof is V 1-x M x O 2 (M: Mg or Al).
However, as in Patent Document 1, as shown in FIG. 8 (Example 10), the vanadium dioxide powder has a change in light transmittance on the longer wavelength side than about 600 nm (mainly in the infrared light region). ), Even if it is applied as a thermochromic material, it cannot fully exert its effect, and it is also difficult to visually perceive the thermochromic phenomenon.
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、可視光領域において温度変化により光透過率を変化させるとともに、赤外光領域において温度変化による光透過率の変化幅をより増加させる二酸化バナジウム含有粒子及びこれを含有するサーモクロミックフィルム、並びに二酸化バナジウム含有粒子の製造方法を提供することである。 The present invention has been made in view of the above problems and situations, and the problem to be solved thereof is to change the light transmittance due to a temperature change in the visible light region and to change the light transmittance due to a temperature change in the infrared light region. It is an object of the present invention to provide vanadium dioxide-containing particles having a higher width, a thermochromic film containing the same, and a method for producing vanadium dioxide-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、元素Ａとしてマグネシウム又はベリリウムを含有し、元素Ｂとしてタングステン及びモリブデンを含有し、バナジウム（１００ａｔｏｍ％）に対し、元素Ａ及び元素Ｂの総含有量が特定範囲内であることにより、可視光領域において温度変化により光透過率を変化させるとともに、赤外光領域において温度変化による光透過率の変化幅をより増加させる二酸化バナジウム含有粒子及びこれを含有するサーモクロミックフィルム、並びに二酸化バナジウム含有粒子の製造方法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 problems, the present inventor contains magnesium or beryllium as the element A, tungsten and molybdenum as the element B, and vanadium (100 atom%) in the process of examining the cause of the problem. On the other hand, when the total contents of the element A and the element B are within the specific range, the light transmission rate is changed by the temperature change in the visible light region, and the change width of the light transmission rate due to the temperature change in the infrared light region. It has been found that a method for producing vanadium dioxide-containing particles, a thermochromic film containing the same, and vanadium dioxide-containing particles can be provided, and the present invention has been made.
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 above-mentioned problem according to the present invention is solved by the following means.
１．サーモクロミック性を有する二酸化バナジウム含有粒子であって、
元素Ａとしてマグネシウム又はベリリウムを含有し、元素Ｂとしてタングステン及びモリブデンを含有し、
バナジウム（１００ａｔｏｍ％）に対し、前記元素Ａの総含有量が０．５～２０ａｔｏｍ％の範囲内であり、かつ、前記元素Ｂの総含有量が０．０５～２０ａｔｏｍ％の範囲内であることを特徴とする二酸化バナジウム含有粒子。
1. 1. Vanadium dioxide-containing particles with thermochromic properties.
It contains magnesium or beryllium as element A and tungsten and molybdenum as element B.
The total content of the element A is in the range of 0.5 to 20 atom% with respect to vanadium (100 atom%), and the total content of the element B is in the range of 0.05 to 20 atom%. Vanadium dioxide-containing particles characterized by.
２．第１項に記載の二酸化バナジウム含有粒子を含有することを特徴とするサーモクロミックフィルム。 2 . A thermochromic film comprising the vanadium dioxide-containing particles according to item 1.
３．１５℃及び７０℃における波長１０００ｎｍ、１１００ｎｍ及び１２００ｎｍでの光透過率を測定し、各波長での１５℃及び７０℃における光透過率の差を算出し、それらを加算して得た光透過率差の加算値が８０％以上であり、かつ前記１５℃から７０℃への温度変化に伴う色差ΔＥ＊ａｂが、下記式（１）を満たすことを特徴とする第２項に記載のサーモクロミックフィルム。 3 . The light transmittance at wavelengths of 1000 nm and 1100 nm and 1200 nm at 15 ° C. and 70 ° C. was measured, the difference in light transmittance at 15 ° C. and 70 ° C. at each wavelength was calculated, and the light transmittance obtained by adding them together. The thermochromic according to the second item, wherein the added value of the difference is 80% or more, and the color difference ΔE * ab accompanying the temperature change from 15 ° C. to 70 ° C. satisfies the following formula (1). the film.
４．０≦ΔＥ＊ａｂ≦６．５・・・（１）4.0 ≤ ΔE * ab ≤ 6.5 ... (1)
４．サーモクロミック性を有する二酸化バナジウム含有粒子の製造方法であって、
バナジウム含有化合物と、元素Ａとしてマグネシウム又はベリリウムを、元素Ｂとしてタングステン及びモリブデンを含有し、更に水を含有する反応液を調製する工程と、
前記反応液を水熱反応させて、二酸化バナジウム含有粒子を形成する工程と、
を有し、
前記反応液を調製する工程では、バナジウム（１００ａｔｏｍ％）に対し、前記元素Ａの総添加量を０．５～２０ａｔｏｍ％の範囲内とし、かつ、前記元素Ｂの総添加量を０．０５～２０ａｔｏｍ％の範囲内とし、二酸化バナジウム含有粒子を形成する工程では、液温２５０～４５０℃の範囲内、かつ、反応時間１秒～４８時間の範囲内で水熱反応させることを特徴とする二酸化バナジウム含有粒子の製造方法。
4 . A method for producing vanadium dioxide-containing particles having thermochromic properties.
A step of preparing a reaction solution containing a vanadium-containing compound, magnesium or beryllium as the element A, tungsten and molybdenum as the element B, and further containing water.
A step of subjecting the reaction solution to a hydrothermal reaction to form vanadium dioxide-containing particles,
Have,
In the step of preparing the reaction solution, the total amount of the element A added is in the range of 0.5 to 20 atom% with respect to vanadium (100 atom%), and the total amount of the element B added is 0.05 to 0. The step of forming vanadium dioxide-containing particles within the range of 20 atom% is characterized by hydrothermal reaction within a liquid temperature range of 250 to 450 ° C. and a reaction time of 1 second to 48 hours. A method for producing vanadium dioxide-containing particles.
５．前記バナジウム含有化合物が、バナジウム（IV）含有化合物であることを特徴とする第４項に記載の二酸化バナジウム含有粒子の製造方法。 5 . The method for producing vanadium dioxide-containing particles according to Item 4 , wherein the vanadium-containing compound is a vanadium (IV) -containing compound.
本発明の上記手段により、可視光領域において温度変化により光透過率を変化させるとともに、赤外光領域において温度変化による光透過率の変化幅をより増加させる二酸化バナジウム含有粒子及びこれを含有するサーモクロミックフィルム、並びに二酸化バナジウム含有粒子の製造方法を提供することができる。 By the above means of the present invention, vanadium dioxide-containing particles and a thermostat containing the same are used to change the light transmittance due to a temperature change in the visible light region and further increase the change width of the light transmittance due to the temperature change in the infrared light region. A method for producing a chromic film and particles containing vanadium dioxide 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。 Although the mechanism of expression and mechanism of action of the effects of the present invention have not been clarified, it is inferred as follows.
本発明の二酸化バナジウム含有粒子は、元素Ａとしてマグネシウム又はベリリウムを含有し、元素Ｂとしてタングステン及びモリブデンを含有し、バナジウム（１００ａｔｏｍ％）に対し、元素Ａの総含有量が０．５～２０ａｔｏｍ％の範囲内であり、かつ、元素Ｂの総含有量が０．０５～２０ａｔｏｍ％の範囲内であることを特徴とし、これにより、可視光領域において温度変化により光透過率を変化させるとともに、赤外光領域において温度変化による光透過率の変化幅を従来に比してより増加させるというものである。
この機構については解明されていないが、２族元素Ａ及びバナジウム以外の５族又は６族元素Ｂをともにドープすることで、二酸化バナジウムの相転移における構造に変化を与え、これにより、相転移温度よりも低温側での可視光・近赤外光領域の光透過率が増加し、一方で相転移温度よりも高温側での可視光・赤外光領域の光透過率がより低下し、すな
わち、赤外光領域での光透過率変化幅の拡大、可視光領域での光透過率の変化の発生を引き起こし、光学変化が拡大しているものと推測している。
The vanadium dioxide-containing particles of the present invention contain magnesium or beryllium as the element A, tungsten and molybdenum as the element B, and the total content of the element A is 0.5 to 0.5 or more with respect to vanadium (100 atom%). It is characterized in that it is in the range of 20 atom% and the total content of the element B is in the range of 0.05 to 20 atom%, whereby the light transmittance is changed by the temperature change in the visible light region and the light transmittance is changed. In the infrared light region, the range of change in light transmittance due to temperature changes is increased more than before.
Although this mechanism has not been elucidated, doping with Group 2 element A and Group 5 or Group 6 element B other than vanadium changes the structure of vanadium dioxide in the phase transition, thereby changing the phase transition temperature. The light transmittance in the visible / near-infrared region on the lower temperature side increases, while the light transmittance in the visible / infrared region on the higher temperature side than the phase transition temperature decreases, that is, It is presumed that the optical change is expanding due to the expansion of the light transmission rate change width in the infrared light region and the occurrence of the light transmission rate change in the visible light region.
本発明の二酸化バナジウム含有粒子は、元素Ａとしてマグネシウム又はベリリウムを含有し、元素Ｂとしてタングステン及びモリブデンを含有し、バナジウム（１００ａｔｏｍ％）に対し、元素Ａの総含有量が０．５～２０ａｔｏｍ％の範囲内であり、かつ、元素Ｂの総含有量が０．０５～２０ａｔｏｍ％の範囲内であることを特徴とする。この特徴は、各請求項に係る発明に共通する技術的特徴である。 The vanadium dioxide-containing particles of the present invention contain magnesium or beryllium as the element A, tungsten and molybdenum as the element B, and the total content of the element A is 0.5 to 0.5 or more with respect to vanadium (100 atom%). It is characterized in that it is in the range of 20 atom% and the total content of the element B is in the range of 0.05 to 20 atom%. This feature is a technical feature common to the claimed inventions.
本発明の実施態様としては、元素Ｂがタングステン又はモリブデンであり、当該タングステン又はモリブデンの含有量がバナジウム（１００ａｔｏｍ％）に対し、０．５～１０ａｔｏｍ％の範囲内であることが好ましい。元素Ｂの含有量が上記範囲内であれば、熱に伴う可視光部の光学変化が大きくなり、元素Ｂが不純物として結晶規則性の低下原因となりにくくサーモクロミック性（光学変化）を維持することができる。 In an embodiment of the present invention, the element B is preferably tungsten or molybdenum, and the content of the tungsten or molybdenum is preferably in the range of 0.5 to 10 atom% with respect to vanadium (100 atom%). When the content of the element B is within the above range, the optical change in the visible light portion due to heat becomes large, and the element B is less likely to cause a decrease in crystal regularity as an impurity and maintains the thermochromic property (optical change). Can be done.
また、元素Ａがマグネシウムであり、当該マグネシウムの含有量がバナジウム（１００ａｔｏｍ％）に対し、０．５～１０ａｔｏｍ％の範囲内であることが好ましい。元素Ａの含有量が上記範囲内であれば、熱に伴う可視光部の光学変化が大きくなり、元素Ａが不純物として結晶規則性の低下原因となりにくくサーモクロミック性（光学変化）を維持することができる。 Further, it is preferable that the element A is magnesium and the content of the magnesium is in the range of 0.5 to 10 atom% with respect to vanadium (100 atom%). When the content of the element A is within the above range, the optical change in the visible light portion due to heat becomes large, and the element A is less likely to cause a decrease in crystal regularity as an impurity and maintains the thermochromic property (optical change). Can be done.
本発明は、上記二酸化バナジウム含有粒子を含有するサーモクロミックフィルムを提供することができる。 The present invention can provide a thermochromic film containing the vanadium dioxide-containing particles.
また、本発明のサーモクロミックフィルムは、１５℃から７０℃への温度変化に伴う色差ΔＥ＊ａｂが式（１）を満たすことが好ましい。Further, in the thermochromic film of the present invention, it is preferable that the color difference ΔE * ab accompanying the temperature change from 15 ° C. to 70 ° C. satisfies the formula (1).
本発明は、サーモクロミック性を有する二酸化バナジウム含有粒子の製造方法であって、バナジウム含有化合物と、元素周期表の２族から選ばれる元素Ａと、バナジウムを除く元素周期表の５族又は６族から選ばれる元素Ｂと、水とを含む反応液を調製する工程と、反応液を水熱反応させて、二酸化バナジウム含有粒子を形成する工程と、を有し、反応液を調製する工程では、バナジウム（１００ａｔｏｍ％）に対し、元素Ａの総添加量を０．５～２０ａｔｏｍ％の範囲内とし、かつ、元素Ｂの総添加量を０．０５～２０ａｔｏｍ％の範囲内とする二酸化バナジウム含有粒子の製造方法を提供することができる。 The present invention is a method for producing vanadium dioxide-containing particles having thermochromic properties, wherein the vanadium-containing compound, element A selected from Group 2 of the Periodic Table of the Elements, and Group 5 or Group 6 of the Periodic Table of the Elements excluding vanadium. The step of preparing the reaction solution includes a step of preparing a reaction solution containing the element B selected from the above elements B and water, and a step of reacting the reaction solution with water and heat to form vanadium dioxide-containing particles. Vanadium dioxide-containing particles having the total amount of element A added in the range of 0.5 to 20 atom% and the total amount of element B added in the range of 0.05 to 20 atom% with respect to vanadium (100 atom%). Production method can be provided.
また、結晶規則性の低下抑制の観点から、バナジウム含有化合物がバナジウム（IV）含有化合物であることが好ましい。 Further, from the viewpoint of suppressing the decrease in crystal regularity, the vanadium-containing compound is preferably a vanadium (IV) -containing compound.
また、結晶規則性を向上させ、転移温度幅をより狭くする観点から、二酸化バナジウム含有粒子を形成する工程では、液温２５０～４５０℃の範囲内、かつ、反応時間１秒～４８時間の範囲内で水熱反応させることが好ましい。 Further, from the viewpoint of improving the crystal regularity and narrowing the transition temperature range, in the step of forming the vanadium dioxide-containing particles, the liquid temperature is in the range of 250 to 450 ° C. and the reaction time is in the range of 1 second to 48 hours. It is preferable to make a water-heat reaction within.
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 constituent elements, and modes and embodiments for carrying out the present invention will be described in detail. In the present application, "-" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
《二酸化バナジウム含有粒子（ＶＯ２含有粒子）》
本発明のサーモクロミック性を有する二酸化バナジウム含有粒子は、元素Ａとしてマグネシウム又はベリリウムを含有し、元素Ｂとしてタングステン及びモリブデンを含有し、バナジウム（１００ａｔｏｍ％）に対し、元素Ａの総含有量が０．５～２０ａｔｏｍ％の範囲内であり、かつ、元素Ｂの総含有量が０．０５～２０ａｔｏｍ％の範囲内であることを特徴とする。
<< Vanadium dioxide-containing particles (VO2 - containing particles) >>
The vanadium dioxide-containing particles having thermochromic properties of the present invention contain magnesium or beryllium as element A, tungsten and molybdenum as element B, and the total content of element A with respect to vanadium (100 atom%). Is in the range of 0.5 to 20 atom%, and the total content of the element B is in the range of 0.05 to 20 atom%.
元素Ａとしては、元素周期表の２族から選ばれる元素であれば特に制限されず、また、１種単独で用いてもよく、２種以上を混合して用いてもよい。２種以上を混合して用いる場合、元素周期表の２族元素の総含有量が０．５～２０ａｔｏｍ％の範囲内になっていればよい。元素周期表の２族元素の総含有量は、好ましくは０．５～１５ａｔｏｍ％の範囲内であり、より好ましくは１．０～１２ａｔｏｍ％の範囲内であり、特に好ましくは５．０～１０ａｔｏｍ％の範囲内である。
中でも、元素Ａとしては、マグネシウム（Ｍｇ）であることが好ましく、この際の含有量としては、バナジウム（１００ａｔｏｍ％）に対し、０．５～１０ａｔｏｍ％の範囲内であることが好ましい。マグネシウムの含有量が０．５ａｔｏｍ％以上であれば、マグネシウムが粒子内に取り込まれる量として十分であり、温度変化による可視光領域の光学変化が大きくなり、含有量が１０ａｔｏｍ％以下であれば添加した金属が不純物として結晶規則性の低下原因となりにくく、サーモクロミック性（光学変化）の低下を抑制することができる。The element A is not particularly limited as long as it is an element selected from Group 2 of the Periodic Table of the Elements, and may be used alone or in combination of two or more. When two or more kinds are mixed and used, the total content of Group 2 elements in the Periodic Table of the Elements may be in the range of 0.5 to 20 atom%. The total content of Group 2 elements in the Periodic Table of the Elements is preferably in the range of 0.5 to 15 atom%, more preferably in the range of 1.0 to 12 atom%, and particularly preferably in the range of 5.0 to 10 atom. It is within the range of%.
Among them, the element A is preferably magnesium (Mg), and the content at this time is preferably in the range of 0.5 to 10 atom% with respect to vanadium (100 atom%). If the magnesium content is 0.5 atom% or more, the amount of magnesium incorporated into the particles is sufficient, the optical change in the visible light region due to temperature changes becomes large, and if the content is 10 atom% or less, it is added. The metal is less likely to cause a decrease in crystal regularity as an impurity, and a decrease in thermochromic property (optical change) can be suppressed.
元素Ｂとしては、バナジウムを除く元素周期表の５族又は６族から選ばれる元素であれば特に制限されず、また、１種単独で用いてもよく、２種以上を混合して用いてもよい。２種以上を混合して用いる場合、バナジウムを除く元素周期表の５族又は６族元素の総含有量が０．０５～２０ａｔｏｍ％の範囲内になっていればよい。バナジウムを除く元素周期表の５族又は６族から選ばれる元素の総含有量は、好ましくは０．５～１０ａｔｏｍ％の範囲内であり、より好ましくは０．７～５．０ａｔｏｍ％の範囲内であり、特に好ましくは１．０～３．０ａｔｏｍ％の範囲内である。
中でも、元素Ｂとしては、タングステン（Ｗ）又はモリブデン（Ｍｏ）であることが好ましく、タングステンとモリブデンとを併用することがより好ましい。いずれの場合においても、それぞれの好ましい含有量としては、バナジウム（１００ａｔｏｍ％）に対し、タングステンについては０．５～１０ａｔｏｍ％の範囲内、モリブデンについては０．５～１０ａｔｏｍ％の範囲内である。タングステン又はモリブデンの含有量が０．５ａｔｏｍ％以上であれば、タングステン又はモリブデンが粒子内に取り込まれる量として十分であり、温度変化による可視光領域の光学変化が大きくなり、含有量が１０ａｔｏｍ％以下であれば添加した金属が不純物として結晶規則性の低下原因となりにくく、サーモクロミック性（光学変化）の低下を抑制することができる。The element B is not particularly limited as long as it is an element selected from Group 5 or Group 6 of the Periodic Table of the Elements excluding vanadium, and may be used alone or in combination of two or more. good. When two or more kinds are mixed and used, the total content of Group 5 or Group 6 elements in the Periodic Table of the Elements excluding vanadium may be in the range of 0.05 to 20 atom%. The total content of the elements selected from Group 5 or Group 6 of the Periodic Table of the Elements excluding vanadium is preferably in the range of 0.5 to 10 atom%, more preferably in the range of 0.7 to 5.0 atom%. It is particularly preferably in the range of 1.0 to 3.0 atom%.
Among them, the element B is preferably tungsten (W) or molybdenum (Mo), and it is more preferable to use tungsten and molybdenum in combination. In each case, the preferable content of each is in the range of 0.5 to 10 atom% for tungsten and in the range of 0.5 to 10 atom% for molybdenum with respect to vanadium (100 atom%). If the content of tungsten or molybdenum is 0.5 atom% or more, the amount of tungsten or molybdenum incorporated into the particles is sufficient, the optical change in the visible light region due to a temperature change becomes large, and the content is 10 atom% or less. If this is the case, the added metal is unlikely to cause a decrease in crystal regularity as an impurity, and a decrease in thermochromic property (optical change) can be suppressed.
〈サーモクロミック性（ＴＣ性）〉
本発明の二酸化バナジウム含有粒子のサーモクロミック性としては、光透過率差の加算値が８０％以上であることが好ましく、９０％以上であることがより好ましく、１００％以上であることが特に好ましい。
光透過率差の加算値は、二酸化バナジウム含有粒子を含むフィルムを１５℃及び７０℃の各条件下において波長１０００ｎｍ、１１００ｎｍ及び１２００ｎｍでの光透過率を測定し、各波長での１５℃及び７０℃における光透過率の差を算出し、それらを加算することにより算出することができる。光透過率の測定は、分光光度計Ｖ－６７０（日本分光（株）製）に温調ユニット（日本分光（株）製）を取り付けて行う。<Thermochromic (TC)>
As for the thermochromic property of the vanadium dioxide-containing particles of the present invention, the added value of the light transmittance difference is preferably 80% or more, more preferably 90% or more, and particularly preferably 100% or more. ..
The added value of the light transmittance difference is obtained by measuring the light transmittance of a film containing vanadium dioxide-containing particles at wavelengths of 1000 nm, 1100 nm and 1200 nm under each condition of 15 ° C. and 70 ° C., and 15 ° C. and 70 at each wavelength. It can be calculated by calculating the difference in light transmittance at ° C and adding them. The light transmittance is measured by attaching a temperature control unit (manufactured by JASCO Corporation) to a spectrophotometer V-670 (manufactured by JASCO Corporation).
〈二酸化バナジウム含有粒子の平均粒径〉
二酸化バナジウム含有粒子の平均粒径は、５～５０ｎｍの範囲内であることが好ましい。二酸化バナジウム含有粒子の平均粒径は、粒子を走査型電子顕微鏡で撮影し、粒子の投影面積と等しい面積を有する円の直径を粒径と定義し、１００個の二酸化バナジウム含有粒子について測定し、これらの算術平均値を求め、これを平均粒径とする。<Average particle size of vanadium dioxide-containing particles>
The average particle size of the vanadium dioxide-containing particles is preferably in the range of 5 to 50 nm. The average particle size of vanadium dioxide-containing particles is measured for 100 vanadium dioxide-containing particles by photographing the particles with a scanning electron microscope, defining the diameter of a circle having an area equal to the projected area of the particles as the particle size. Obtain these arithmetic average values and use this as the average particle size.
二酸化バナジウム含有粒子の粒径分布のメディアン径（Ｄ５０）は、１５０ｎｍ以下であることが好ましい。
二酸化バナジウム含有粒子の粒径分布のメディアン径（Ｄ５０）は、調製した水熱反応後の各分散液（詳細は後述する。）を、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、回折／散乱光強度で３５～７５％（絶対値では、７００～１５００）の間になるように希釈した後、粒径の指標として二酸化バナジウム含有粒子の粒径Ｄ５０を測定することができる。測定値は、体積換算値を使用する。Ｄ５０の値が小さいほど粒径が小さいことを表す。The median diameter (D50) of the particle size distribution of the vanadium dioxide-containing particles is preferably 150 nm or less.
The median diameter (D50) of the particle size distribution of the vanadium dioxide-containing particles is determined by using a laser diffraction type particle size distribution measuring device manufactured by Shimadzu Corporation for each dispersion liquid (details will be described later) after the hydrothermal reaction prepared. After diluting so that the diffraction / scattered light intensity is between 35 and 75% (700 to 1500 in absolute value), the particle size D50 of the vanadium dioxide-containing particles can be measured as an index of the particle size. For the measured value, the volume conversion value is used. The smaller the value of D50, the smaller the particle size.
《二酸化バナジウム含有粒子の製造方法》
本発明の二酸化バナジウム含有粒子の製造方法は、バナジウム含有化合物と、元素Ａとしてマグネシウム又はベリリウムを、元素Ｂとしてタングステン及びモリブデンを含有し、更に水を含有する反応液を調製する工程と、反応液を水熱反応させて、二酸化バナジウム含有粒子を形成する工程と、を有し、反応液を調製する工程では、バナジウム（１００ａｔｏｍ％）に対し、元素Ａの総添加量を０．５～２０ａｔｏｍ％の範囲内とし、かつ、元素Ｂの総添加量を０．０５～２０ａｔｏｍ％の範囲内とし、二酸化バナジウム含有粒子を形成する工程では、液温２５０～４５０℃の範囲内、かつ、反応時間１秒～４８時間の範囲内で水熱反応させることを特徴とする。
以下に、本発明のサーモクロミック性を有する二酸化バナジウム含有粒子の製造方法について詳細に説明する。
<< Manufacturing method of vanadium dioxide-containing particles >>
The method for producing vanadium dioxide-containing particles of the present invention comprises a step of preparing a reaction solution containing a vanadium-containing compound , magnesium or beryllium as element A, tungsten and molybdenum as element B, and further containing water, and a reaction solution. In the step of forming vanadium dioxide-containing particles and preparing a reaction solution, the total amount of element A added is 0.5 to 20 atom% with respect to vanadium (100 atom%). In the step of forming vanadium dioxide-containing particles, the liquid temperature is within the range of 250 to 450 ° C. and the reaction time is within the range of 0.05 to 20 atom% and the total amount of element B added is within the range of 0.05 to 20 atom%. It is characterized by hydrothermal reaction within the range of 1 second to 48 hours .
Hereinafter, a method for producing vanadium dioxide-containing particles having thermochromic properties according to the present invention will be described in detail.
（１）反応液の調製工程
まず、本発明の二酸化バナジウム含有粒子の製造方法では、バナジウム含有化合物と、元素周期表の２族から選ばれる元素Ａと、バナジウムを除く元素周期表の５族又は６族から選ばれる元素Ｂと、水とを含む反応液を調製する。(1) Preparation Step of Reaction Solution First, in the method for producing vanadium dioxide-containing particles of the present invention, a vanadium-containing compound, element A selected from Group 2 of the Periodic Table of the Elements, and Group 5 of the Periodic Table of the Elements excluding vanadium or A reaction solution containing element B selected from Group 6 and water is prepared.
（バナジウム化合物）
本発明に係るバナジウム含有化合物としては、例えば、五価又は四価のバナジウムを含む化合物が挙げられる。
バナジウム含有化合物として、五価のバナジウムを含む化合物を用いる場合には、後述するようなヒドラジン（Ｎ２Ｈ４）又はその水和物（Ｎ２Ｈ４・ｎＨ２Ｏ）等の還元剤が必要となる。これら還元剤は、還元効果が強く、過還元を起こしやすいため、結晶規則性の低下原因となることから、バナジウム含有化合物としては、四価のバナジウム含有化合物が好ましい。(Vanadium compound)
Examples of the vanadium-containing compound according to the present invention include compounds containing pentavalent or tetravalent vanadium.
When a compound containing pentavalent vanadium is used as the vanadium-containing compound, a reducing agent such as hydrazine (N 2 H 4 ) or a hydrate thereof (N 2 H 4 · nH 2 O) as described later is required. Will be. Since these reducing agents have a strong reducing effect and easily cause overreduction, they cause a decrease in crystal regularity. Therefore, a tetravalent vanadium-containing compound is preferable as the vanadium-containing compound.
五価のバナジウム含有化合物（バナジウム（Ｖ）含有化合物）としては、五酸化二バナジウム（Ｖ２Ｏ５）、バナジン酸アンモニウム（ＮＨ４ＶＯ３）、三塩化酸化バナジウム（ＶＯＣｌ３）、バナジン酸ナトリウム（ＮａＶＯ３）等が挙げられる。
四価のバナジウム含有化合物（バナジウム（IV）含有化合物）としては、シュウ酸バナジル（ＶＯＣ２Ｏ４）、酸化硫酸バナジウム（ＶＯＳＯ４、以下、硫酸バナジルとも称する。）、四酸化二バナジウム（Ｖ２Ｏ４）を硫酸等の酸で溶解したものが挙げられる。
上記バナジウム含有化合物は、原料液中に溶解していてもよく、分散していてもよい。また、バナジウム含有化合物は、１種単独で用いてもよく、２種以上を混合して用いてもよい。また、これらの化合物としては、水和した状態のもの（水和物）を用いてもよい。Examples of the pentavalent vanadium-containing compound (vanadium (V) -containing compound) include divanadium pentoxide (V 2 O 5 ), ammonium vanadate (NH 4 VO 3 ), vanadium trichloride (VOCl 3 ), and sodium vanadate. (NaVO 3 ) and the like can be mentioned.
Examples of the tetravalent vanadium-containing compound (vanadium (IV) -containing compound) include vanadyl oxalate (VOC 2 O 4 ), vanadium oxide sulfate (VOSO 4 , hereinafter also referred to as vanadyl sulfate), and vanadium tetraoxide (V 2 ). Examples thereof include those obtained by dissolving O 4 ) with an acid such as sulfuric acid.
The vanadium-containing compound may be dissolved or dispersed in the raw material liquid. Further, the vanadium-containing compound may be used alone or in combination of two or more. Further, as these compounds, those in a hydrated state (hydrate) may be used.
（添加元素）
反応液を調製する工程では、上記バナジウム含有化合物に加え、元素周期表の２族から選ばれる元素Ａと、バナジウムを除く元素周期表の５族又は６族から選ばれる元素Ｂとを添加することを特徴とする。
元素Ａの総添加量は、バナジウム（１００ａｔｏｍ％）に対し、０．５～２０ａｔｏｍ％の範囲内である。
元素Ｂの総添加量は、バナジウム（１００ａｔｏｍ％）に対し、０．０５～２０ａｔｏｍ％の範囲内である。(Additional element)
In the step of preparing the reaction solution, in addition to the above vanadium-containing compound, element A selected from Group 2 of the Periodic Table of the Elements and element B selected from Group 5 or Group 6 of the Periodic Table of the Elements excluding vanadium are added. It is characterized by.
The total amount of element A added is in the range of 0.5 to 20 atom% with respect to vanadium (100 atom%).
The total amount of element B added is in the range of 0.05 to 20 atom% with respect to vanadium (100 atom%).
反応液に添加する元素Ａ及び元素Ｂの態様としては、単体であってもよいし、本発明の効果を阻害しない範囲において、当該元素Ａ又は元素Ｂを含む化合物であってもよい。 The embodiment of the element A and the element B to be added to the reaction solution may be a simple substance or a compound containing the element A or the element B as long as the effect of the present invention is not impaired.
（水）
本発明に係る水は、特に限定されないが、不純物の少ない高純度のものが好ましく、具体的には、イオン交換水、蒸留水等の精製水を用いることができる。(water)
The water according to the present invention is not particularly limited, but is preferably high-purity water with few impurities, and specifically, purified water such as ion-exchanged water and distilled water can be used.
（還元剤）
本発明に係るバナジウム含有化合物として、五価のバナジウム含有化合物を採用する場合には、還元剤が用いられる。
還元剤は、水に容易に溶解する性質を有し、かつ、五価のバナジウム含有化合物の還元剤として機能すればよく、例えば、ヒドラジン（Ｎ２Ｈ４）、ヒドラジン一水和物などのヒドラジンの水和物（Ｎ２Ｈ４・ｎＨ２Ｏ）などが挙げられる。(Reducing agent)
When a pentavalent vanadium-containing compound is adopted as the vanadium-containing compound according to the present invention, a reducing agent is used.
The reducing agent may have the property of being easily dissolved in water and may function as a reducing agent for a pentavalent vanadium-containing compound. For example, hydrazine (N 2 H 4 ), hydrazine monohydrate and the like. Hydrazine (N 2 H 4 · n H 2 O) and the like can be mentioned.
（その他）
本発明に係る反応液は、酸化性又は還元性を有する物質が更に混ざったものであってよい。このような物質としては、例えば、過酸化水素（Ｈ２Ｏ２）が挙げられる。酸化性又は還元性を有する物質を添加することにより、反応液のｐＨを調整したり、バナジウム含有化合物を均一に溶解させたりすることができる。
なお、過酸化水素としては、例えば、過酸化水素水（濃度３５質量％、和光純薬社製、特級）を好適に用いることができる。(others)
The reaction solution according to the present invention may be further mixed with an oxidizing or reducing substance. Examples of such a substance include hydrogen peroxide (H 2 O 2 ). By adding an oxidizing or reducing substance, the pH of the reaction solution can be adjusted or the vanadium-containing compound can be uniformly dissolved.
As the hydrogen peroxide, for example, hydrogen peroxide solution (concentration 35% by mass, manufactured by Wako Pure Chemical Industries, Ltd., special grade) can be preferably used.
（２）水熱反応工程
次に、調製した反応液を水熱反応させて二酸化バナジウム含有粒子を形成する。
ここで、「反応液を水熱反応させる」とは、反応液に水熱反応処理を施すことをいう。また、「水熱反応」とは、温度及び圧力が水の臨界点（３７４℃、２２ＭＰａ）よりも低い熱水（亜臨界水）中、あるいは温度及び圧力が水の臨界点よりも高い超臨界水中において生じる化学反応を意味する。亜臨界水とは、例えば、温度が１５０～３７４℃の範囲内で、圧力がその温度における飽和水蒸気圧よりも高い状態の水をいう。
水熱反応処理は、例えば、オートクレーブ装置内で実施される。水熱反応処理により、二酸化バナジウム含有粒子が得られる。また、耐圧性の管型又は槽型などのフロー型リアクター（流通型反応器）を用いて亜臨界又は超臨界状態にある高温高圧水と混合して合成する連続法も使用でき、特には管型のリアクターを利用する連続法を好適に利用できる。(2) Hydrothermal reaction step Next, the prepared reaction solution is hydrothermally reacted to form vanadium dioxide-containing particles.
Here, "to make the reaction solution hydrothermally react" means to perform a hydrothermal reaction treatment on the reaction solution. The "hydrothermal reaction" is supercritical water in which the temperature and pressure are lower than the critical point of water (374 ° C., 22 MPa) or in hot water (subcritical water) or the temperature and pressure are higher than the critical point of water. It means a chemical reaction that occurs in water. Sub-critical water refers to water in a state where the temperature is in the range of 150 to 374 ° C. and the pressure is higher than the saturated water vapor pressure at that temperature, for example.
The hydrothermal reaction treatment is carried out, for example, in an autoclave apparatus. Vanadium dioxide-containing particles are obtained by the hydrothermal reaction treatment. In addition, a continuous method of synthesizing by mixing with high-temperature and high-pressure water in a subcritical or supercritical state using a flow-type reactor (flow reactor) such as a pressure-resistant tube-type or tank-type can also be used, and in particular, a tube. A continuous method utilizing a type reactor can be suitably used.
水熱反応処理の条件（反応物の量、処理温度、処理圧力、処理時間）は、適宜設定されるが、水熱反応処理条件としては、液温が２５０～４５０℃の範囲内、かつ、反応時間が１秒～４８時間の範囲内であることが好ましい。反応処理温度及び時間が、上記下限値以上であれば、結晶化が促進され、光学特性変化が大きくかつ転移温度幅をより狭くし、上記上限値以下であれば、粒子間融着による粗大化が低減され、光学特性変化を維持することができる。 The conditions for the hydrothermal reaction treatment (amount of reactant, treatment temperature, treatment pressure, treatment time) are appropriately set, but the conditions for the hydrothermal reaction treatment are such that the liquid temperature is within the range of 250 to 450 ° C. and The reaction time is preferably in the range of 1 second to 48 hours. If the reaction treatment temperature and time are equal to or higher than the above lower limit, crystallization is promoted, the change in optical characteristics is large and the transition temperature width is narrower, and if it is equal to or lower than the upper limit, coarsening due to interparticle fusion occurs. Can be reduced and the change in optical characteristics can be maintained.
なお、本発明において、二酸化バナジウム含有粒子の転移温度幅は、以下のようにして測定される。
まず、二酸化バナジウム含有粒子を含む水分散液を調製し、これを水に溶解したポリビニルアルコール中に混合する。この混合液をＰＥＴフィルム上に塗布し、乾燥後の膜厚が所定の厚さとなるようにワイヤーバーで塗布を行った後、乾燥して、測定用フィルムを作製する。
この測定用フィルムを用いて、１０℃から８５℃まで１℃刻みで温度を変化させ、各温度における波長２０００ｎｍでのそれぞれの光透過率を測定し、転移温度幅を算出する。具体的には、１０℃で測定された光透過率に対し光透過率差が１％以上となる最も低い温度を転移開始温度、８５℃で測定された光透過率に対し光透過率差が１％未満となる温度又は光透過率差が１％未満となる温度がない場合は８５℃を転移終了温度とし、下記式により転移温度幅を算出する。In the present invention, the transition temperature range of the vanadium dioxide-containing particles is measured as follows.
First, an aqueous dispersion containing vanadium dioxide-containing particles is prepared and mixed with polyvinyl alcohol dissolved in water. This mixed solution is applied onto a PET film, applied with a wire bar so that the film thickness after drying becomes a predetermined thickness, and then dried to prepare a measuring film.
Using this measuring film, the temperature is changed from 10 ° C. to 85 ° C. in 1 ° C. increments, the light transmittance at each temperature of 2000 nm is measured, and the transition temperature range is calculated. Specifically, the transition start temperature is the lowest temperature at which the light transmittance difference is 1% or more with respect to the light transmittance measured at 10 ° C., and the light transmittance difference is with respect to the light transmittance measured at 85 ° C. If there is no temperature of less than 1% or a temperature of less than 1% of the light transmittance difference, 85 ° C. is set as the transition end temperature, and the transition temperature range is calculated by the following formula.
転移温度幅（℃）＝転移終了温度－転移開始温度 Transition temperature range (° C) = transition end temperature-transition start temperature
本発明の二酸化バナジウム含有粒子の転移温度幅は、１～２５℃の範囲内であることが好ましい。 The transition temperature range of the vanadium dioxide-containing particles of the present invention is preferably in the range of 1 to 25 ° C.
水熱反応におけるバナジウム含有化合物由来の二酸化バナジウムの固形分濃度は、０．１～２０質量％の範囲内であることが好ましい。
二酸化バナジウムの固形分濃度が、０．１～２０質量％の範囲内であることにより、結晶成長を抑制することができ、分散安定化を図ることができる。The solid content concentration of vanadium dioxide derived from the vanadium-containing compound in the hydrothermal reaction is preferably in the range of 0.1 to 20% by mass.
When the solid content concentration of vanadium dioxide is in the range of 0.1 to 20% by mass, crystal growth can be suppressed and dispersion stabilization can be achieved.
また、水熱反応は、撹拌されながら行われることが、二酸化バナジウム含有粒子の粒径をより均一化できるため、好ましい。
なお、水熱反応処理は、バッチ式で実施してもよく、連続式で実施してもよい。Further, it is preferable that the hydrothermal reaction is carried out with stirring because the particle size of the vanadium dioxide-containing particles can be made more uniform.
The hydrothermal reaction treatment may be carried out in a batch manner or in a continuous manner.
《サーモクロミックフィルム》
本発明のサーモクロミックフィルムは、上記した本発明の二酸化バナジウム含有粒子を含有する。《Thermochromic film》
The thermochromic film of the present invention contains the vanadium dioxide-containing particles of the present invention described above.
本発明のサーモクロミックフィルムは、ＪＩＳ Ｚ ８７８１－４：２０１３に準拠した、フィルム温度１５℃から７０℃への温度変化に伴う色差ΔＥ＊ａｂが、下記式（１）を満たすことが好ましい。In the thermochromic film of the present invention, it is preferable that the color difference ΔE * ab due to the temperature change from the film temperature of 15 ° C. to 70 ° C. according to JIS Z 8781-4: 2013 satisfies the following formula (1).
４．０≦ΔＥ＊ａｂ≦６．５・・・（１）4.0 ≤ ΔE * ab ≤ 6.5 ... (1)
以下、本発明のサーモクロミックフィルムとして、透明基材と光学機能層とを備えたフィルムを例にとって説明するが、特にこれに限定されない。 Hereinafter, as the thermochromic film of the present invention, a film provided with a transparent substrate and an optical functional layer will be described as an example, but the present invention is not particularly limited thereto.
サーモクロミックフィルムは、透明基材と光学機能層とを備え、当該光学機能層が樹脂と上記した本発明の二酸化バナジウム含有粒子とを含有することが好ましい態様である。 It is preferable that the thermochromic film includes a transparent base material and an optical functional layer, and the optical functional layer contains a resin and the above-mentioned vanadium dioxide-containing particles of the present invention.
サーモクロミックフィルムに適用可能な透明基材としては、透明であれば特に制限はなく、ガラス、石英、透明樹脂フィルム等を挙げることができるが、フレキシブル性の付与や生産適性（ロールｔｏロール適性）の観点から、透明樹脂フィルムであることが好ましい。本発明でいう透明基材における「透明」とは、可視光領域における平均光線透過率が５０％以上であることをいい、好ましくは６０％以上、より好ましくは７０％以上、特に好ましくは８０％以上である。 The transparent base material applicable to the thermochromic film is not particularly limited as long as it is transparent, and examples thereof include glass, quartz, and a transparent resin film, but imparting flexibility and suitability for production (roll-to-roll suitability). From the viewpoint of the above, a transparent resin film is preferable. "Transparent" in the transparent substrate in the present invention means that the average light transmittance in the visible light region is 50% or more, preferably 60% or more, more preferably 70% or more, and particularly preferably 80%. That is all.
透明基材の厚さは、３０～２００μｍの範囲内であることが好ましく、より好ましくは３０～１００μｍの範囲内であり、更に好ましくは３５～７０μｍでの範囲内である。透明基材の厚さが３０μｍ以上であれば、取扱い中にシワ等が発生しにくくなり、また、厚さが２００μｍ以下であれば、合わせガラス作製時、ガラス基材と貼り合わせる際のガラス曲面への追従性がよくなる。 The thickness of the transparent substrate is preferably in the range of 30 to 200 μm, more preferably in the range of 30 to 100 μm, and further preferably in the range of 35 to 70 μm. If the thickness of the transparent base material is 30 μm or more, wrinkles and the like are less likely to occur during handling, and if the thickness is 200 μm or less, the curved surface of the glass when the laminated glass is manufactured and the glass base material is bonded. The followability to is improved.
透明基材は、サーモクロミックフィルムのシワの発生を防止する観点から、温度１５０℃において、熱収縮率が０．１～３．０％の範囲内であることが好ましく、１．５～３．０％の範囲内であることがより好ましく、１．９～２．７％の範囲内であることが更に好ましい。 From the viewpoint of preventing the occurrence of wrinkles in the thermochromic film, the transparent substrate preferably has a heat shrinkage rate in the range of 0.1 to 3.0% at a temperature of 150 ° C., and is preferably 1.5 to 3. It is more preferably in the range of 0%, further preferably in the range of 1.9 to 2.7%.
サーモクロミックフィルムに適用可能な透明基材としては、上述のように、透明であれば特に制限されず種々の透明樹脂フィルムを用いることができるが、例えば、ポリオレフィンフィルム（例えば、ポリエチレンフィルム、ポリプロピレンフィルム等）、ポリエステルフィルム（例えば、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム等）、ポリ塩化ビニルフィルム、トリアセチルセルロースフィルム等を用いることができ、好ましくはポリエステルフィルム、トリアセチルセルロースフィルムであり、より好ましくはポリエステルフィルムである。 As the transparent base material applicable to the thermochromic film, as described above, various transparent resin films can be used as long as they are transparent. For example, a polyolefin film (for example, a polyethylene film or a polypropylene film) can be used. Etc.), polyester film (for example, polyethylene terephthalate film, polyethylene naphthalate film, etc.), polyvinyl chloride film, triacetyl cellulose film and the like can be used, preferably polyester film and triacetyl cellulose film, and more preferably. It is a polyester film.
透明樹脂フィルムとしては、二軸配向ポリエステルフィルムであることが特に好ましいが、未延伸又は少なくとも一方に延伸された一軸延伸ポリエステルフィルムを用いることもできる。強度向上、熱膨張抑制の点から延伸フィルムが好ましい。特に、サーモクロミックフィルムを具備した合わせガラスが、自動車のフロントガラスとして用いられる場合には、延伸フィルムがより好ましい。 The transparent resin film is particularly preferably a biaxially oriented polyester film, but an unstretched or at least one stretched uniaxially stretched polyester film can also be used. A stretched film is preferable from the viewpoint of improving strength and suppressing thermal expansion. In particular, when a laminated glass provided with a thermochromic film is used as a windshield of an automobile, a stretched film is more preferable.
透明基材として透明樹脂フィルムを用いる場合、取り扱いを容易にするために、透明性を損なわない範囲内で微粒子を含有させてもよい。当該透明樹脂フィルムに適用可能な微粒子としては、例えば、炭酸カルシウム、リン酸カルシウム、シリカ、カオリン、タルク、二酸化チタン、アルミナ、硫酸バリウム、フッ化カルシウム、フッ化リチウム、ゼオライト、硫化モリブデン等の無機微粒子や、架橋高分子微粒子、シュウ酸カルシウム等の有機微粒子を挙げることができる。
微粒子を添加する方法としては、透明樹脂フィルムを形成する原料としての樹脂（例えば、ポリエステル等）中に、微粒子を含有させる方法、押出機に直接添加する方法等を挙げることができ、このうちいずれか一方の方法を採用してもよく、二つの方法を併用してもよい。透明樹脂フィルムには必要に応じて上記微粒子の他にも各種添加剤を加えてもよい。このような添加剤としては、例えば、安定剤、潤滑剤、架橋剤、ブロッキング防止剤、酸化防止剤、染料、顔料、紫外線吸収剤等が挙げられる。When a transparent resin film is used as the transparent base material, fine particles may be contained within a range that does not impair the transparency in order to facilitate handling. Examples of fine particles applicable to the transparent resin film include inorganic fine particles such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide. , Cross-linked polymer fine particles, organic fine particles such as calcium oxalate can be mentioned.
Examples of the method of adding fine particles include a method of incorporating fine particles in a resin (for example, polyester) as a raw material for forming a transparent resin film, a method of adding fine particles directly to an extruder, and the like. Either method may be adopted, or the two methods may be used in combination. Various additives may be added to the transparent resin film in addition to the above fine particles, if necessary. Examples of such additives include stabilizers, lubricants, cross-linking agents, blocking inhibitors, antioxidants, dyes, pigments, ultraviolet absorbers and the like.
透明基材上には、樹脂及び本発明の二酸化バナジウム含有粒子を含有する光学機能層が設けられる。 An optical functional layer containing a resin and vanadium dioxide-containing particles of the present invention is provided on the transparent substrate.
ここで、樹脂としては、特に制限されず、広く一般にサーモクロミックフィルム（光学フィルム）の光学機能層に使用されるものと同様の樹脂が使用でき、好ましくは水溶性高分子が使用できる。ここでいう「水溶性高分子」とは、２５℃の水１００ｇに０．００１ｇ以上溶解する高分子のことをいう。
水溶性高分子の具体例としては、ポリビニルアルコール、ポリエチレンイミン、ゼラチン（例えば、特開２００６－３４３３９１号公報記載のゼラチンを代表とする親水性高分子）、デンプン、グアーガム、アルギン酸塩、メチルセルロース、エチルセルロース、ヒドロキシアルキルセルロース、カルボキシアルキルセルロース、ポリ（メタ）アクリルアミド、ポリエチレンイミン、ポリエチレングリコール、ポリアルキレンオキサイド、ポリビニルピロリドン（ＰＶＰ）、ポリビニルメチルエーテル、カルボキシビニルポリマー、ポリ（メタ）アクリル酸、ポリ（メタ）アクリル酸ナトリウム、ナフタリンスルホン酸縮合物や、アルブミン、カゼイン等の蛋白質、アルギン酸ソーダ、デキストリン、デキストラン、デキストラン硫酸塩等の糖誘導体等を挙げることができる。Here, the resin is not particularly limited, and a resin similar to that generally used for the optical functional layer of a thermochromic film (optical film) can be used, and a water-soluble polymer can be preferably used. The term "water-soluble polymer" as used herein refers to a polymer that dissolves 0.001 g or more in 100 g of water at 25 ° C.
Specific examples of the water-soluble polymer include polyvinyl alcohol, polyethyleneimine, gelatin (for example, a hydrophilic polymer represented by gelatin described in JP-A-2006-343391), starch, guar gum, alginate, methyl cellulose, and ethyl cellulose. , Hydroxyalkyl cellulose, Carboxyalkyl cellulose, Poly (meth) acrylamide, Polyethyleneimine, Polyethylene glycol, Polyalkylene oxide, Polyvinylpyrrolidone (PVP), Polyvinylmethyl ether, Carboxyvinyl polymer, Poly (meth) acrylic acid, Poly (meth) Examples thereof include proteins such as sodium acrylate and naphthalin sulfonic acid condensate, albumin and casein, and sugar derivatives such as sodium alginate, dextrin, dextran and dextran sulfate.
光学機能層における二酸化バナジウム含有粒子の含有量は、所望のサーモクロミック性を得る観点から、光学機能層の総質量（１００質量％）に対して１～６０質量％の範囲内であることが好ましく、５～５０質量％の範囲内であることがより好ましい。 The content of the vanadium dioxide-containing particles in the optical functional layer is preferably in the range of 1 to 60% by mass with respect to the total mass (100% by mass) of the optical functional layer from the viewpoint of obtaining desired thermochromic properties. It is more preferably in the range of 5 to 50% by mass.
光学機能層には、目的とする効果を損なわない範囲で、従来公知の各種添加剤を使用することができる。適用可能な各種の添加剤を、以下に列挙する。例えば、特開昭５７－７４１９３号公報、特開昭５７－８７９８８号公報及び特開昭６２－２６１４７６号公報に記載の紫外線吸収剤、特開昭５７－７４１９２号公報、特開昭５７－８７９８９号公報、特開昭６０－７２７８５号公報、特開昭６１－１４６５９１号公報、特開平１－９５０９１号公報及び特開平３－１３３７６号公報等に記載の退色防止剤、アニオン、カチオン又はノニオンの各種界面活性剤、特開昭５９－４２９９３号公報、特開昭５９－５２６８９号公報、特開昭６２－２８００６９号公報、特開昭６１－２４２８７１号公報及び特開平４－２１９２６６号公報等に記載の蛍光増白剤、硫酸、リン酸、酢酸、クエン酸、水酸化ナトリウム、水酸化カリウム、炭酸カリウム等のｐＨ調整剤、消泡剤、ジエチレングリコール等の潤滑剤、防腐剤、防黴剤、帯電防止剤、マット剤、熱安定剤、酸化防止剤、難燃剤、結晶核剤、無機粒子、有機粒子、減粘剤、滑剤、赤外線吸収剤、色素、顔料等の公知の各種添加剤等が挙げられる。 Various conventionally known additives can be used for the optical functional layer as long as the desired effect is not impaired. The various additives that are applicable are listed below. For example, the ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, JP-A-57-74192, JP-A-57-87989. No. 60-72785, Japanese Patent Application Laid-Open No. 61-146591, Japanese Patent Application Laid-Open No. 1-95091, Japanese Patent Application Laid-Open No. 3-13376, etc. Various surfactants, JP-A-59-4-2793, JP-A-59-52689, JP-A-62-28069, JP-A-61-242871, JP-A-4-219266, etc. Described fluorescent whitening agents, pH adjusters such as sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, defoaming agents, lubricants such as diethylene glycol, preservatives, fungicides, etc. Various known additives such as antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, thickeners, lubricants, infrared absorbers, dyes, pigments, etc. Can be mentioned.
サーモクロミックフィルムの製造方法（光学機能層の形成方法）としては、特に制限されず、本発明の二酸化バナジウム含有粒子を使用する以外は、公知の方法と同様にして又は適宜変更して適用できる。具体的には、二酸化バナジウム含有粒子を含む塗布液を調製し、当該塗布液を湿式塗布方式により透明基材上に塗布、乾燥して光学機能層を形成する方法が好ましい。 The method for producing the thermochromic film (method for forming the optical functional layer) is not particularly limited, and can be applied in the same manner as or appropriately modified from the known method except that the vanadium dioxide-containing particles of the present invention are used. Specifically, a method of preparing a coating liquid containing vanadium dioxide-containing particles, applying the coating liquid on a transparent substrate by a wet coating method, and drying to form an optical functional layer is preferable.
上記方法において、湿式塗布方式としては、特に制限されず、例えば、ロールコーティング法、ロッドバーコーティング法、エアナイフコーティング法、スプレーコーティング法、スライド型カーテン塗布法、又は米国特許第２７６１４１９号明細書、米国特許第２７６１７９１号明細書等に記載のスライドホッパー塗布法、エクストルージョンコート法等が挙げられる。 In the above method, the wet coating method is not particularly limited, and is, for example, a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a slide type curtain coating method, or U.S. Pat. No. 2,761419, U.S.A. Examples thereof include the slide hopper coating method and the extrusion coat method described in Japanese Patent No. 2761791.
《分散液》
本発明の二酸化バナジウム含有粒子を水に分散させた場合、優れたサーモクロミック性を示す、二酸化バナジウム含有粒子を含有する分散液を提供することができる。この二酸化バナジウム含有粒子を含有する分散液を塗布すれば、優れたサーモクロミック性を示すサーモクロミックフィルム等を提供することができる。
分散させるための溶媒は、水を含んでいればよく、二酸化バナジウムの機能を阻害しない範囲で有機溶媒等の公知の溶媒を使用することができる。
ＶＯ２含有粒子を含む水分散液のサーモクロミック性は、例えば、分光光度計Ｖ－６７０（日本分光株式会社製）を用いて、水の吸収ピークによる影響を受けない波長２０００ｎｍにおける光透過率の差として測定することができる。《Dispersion》
When the vanadium dioxide-containing particles of the present invention are dispersed in water, it is possible to provide a dispersion liquid containing the vanadium dioxide-containing particles exhibiting excellent thermochromic properties. By applying the dispersion liquid containing the vanadium dioxide-containing particles, it is possible to provide a thermochromic film or the like exhibiting excellent thermochromic properties.
The solvent for dispersion may contain water, and a known solvent such as an organic solvent can be used as long as the function of vanadium dioxide is not impaired.
The thermochromic property of the aqueous dispersion containing VO2 - containing particles was determined by using, for example, a spectrophotometer V-670 (manufactured by Nippon Spectroscopy Co., Ltd.) with a light transmittance at a wavelength of 2000 nm, which is not affected by the absorption peak of water. It can be measured as a difference.
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、実施例における元素Ａ及び元素Ｂの添加量（ａｔｏｍ％）は、反応液中のバナジウム（１００ａｔｏｍ％）に対する値である。また、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。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. The amount of element A and element B added (atom%) in the examples is a value with respect to vanadium (100 atom%) in the reaction solution. In addition, although the display of "%" is used in the examples, it represents "mass%" unless otherwise specified.
《分散液の調製》
以下のようにして、二酸化バナジウム含有粒子を含む分散液１０１～１３５を調製した。<< Preparation of dispersion >>
〈分散液１０１の調製〉
過酸化水素水（濃度３５質量％、和光純薬社製）の１０質量％水溶液５０ｍＬに、五酸化バナジウム（Ｖ２Ｏ５、和光純薬社製、特級）１．５ｇと、元素Ｂとしてタングステン１．００ａｔｏｍ％（（ＮＨ４）１０Ｗ１２Ｏ４、和光純薬社製、８５．０＋％ ａｓ ＷＯ３）とを添加し、これを４時間撹拌して澄んだ赤茶色のゾルを得た。
得られたゾルに、還元剤であるヒドラジン一水和物（Ｎ２Ｈ４・Ｈ２Ｏ、和光純薬社製、特級）の５質量％水溶液をゆっくり滴下し、ｐＨが４．５の反応液（液温２５℃）とした後、純水を加えて二酸化バナジウム換算で固形分が２．５質量％となるように調製した。
調製した反応液を、市販の水熱反応処理用オートクレーブ（三愛科学社製、ＨＵ－５０型（ＳＵＳ製本体に５０ｍＬ容積のテフロン（登録商標）製内筒を備える。））内に入れ、２７０℃、５．５１ＭＰａで２４時間、水熱反応させ、二酸化バナジウム含有粒子を含む分散液１０１を調製した。<Preparation of
Vanadium pentoxide ( V2O 5 , Wako Pure Chemical Industries, Ltd., special grade) 1.5 g and tungsten as element B in 50 mL of a 10 mass% aqueous solution of hydrogen peroxide solution (concentration 35 mass%, manufactured by Wako Pure Chemical Industries, Ltd.) 1.00 atom% ((NH 4 ) 10 W 12 O 4 , manufactured by Wako Pure Chemical Industries, Ltd., 85.0 +% as WO 3 ) was added, and this was stirred for 4 hours to obtain a clear reddish brown sol. ..
A 5% by mass aqueous solution of hydrazine monohydrate ( N2 H4, H2O , manufactured by Wako Pure Chemical Industries, Ltd., special grade) as a reducing agent is slowly added dropwise to the obtained sol, and a reaction with a pH of 4.5 is performed. After making a liquid (liquid temperature 25 ° C.), pure water was added to prepare the solid content to be 2.5% by mass in terms of vanadium dioxide.
The prepared reaction solution is placed in a commercially available autoclave for hydrothermal reaction treatment (manufactured by San-ai Kagaku Co., Ltd., HU-50 type (a SUS main body is provided with a 50 mL volume Teflon (registered trademark) inner cylinder)) and 270. A
〈分散液１０２～１０９の調製〉
分散液１０１の調製において、元素Ａ及び元素Ｂの種類及び添加量を表Ｉに記載のとおりに変更した以外は同様にして、分散液１０２～１０９を調製した。各分散液の調製に用いた、元素Ａあるいは元素Ｂを含む化合物は、下記のとおりである。
なお、分散液１０３及び１０４では、添加元素としてモリブデンに加えナトリウム（１族）、イットリウム（３族）をそれぞれ添加し、分散液１０５では、添加元素としてベリリウムに加えイットリウム（３族）を添加した。<Preparation of
In the preparation of the
In the
マグネシウム：ＭｇＳＯ４、和光純薬製、９８．０＋％
ベリリウム：ＢｅＳＯ４・ｎＨ２Ｏ、和光純薬製、５０．０＋％（無水物として）
タングステン：（ＮＨ４）１０Ｗ１２Ｏ４、和光純薬社製、８５．０＋％ ａｓ ＷＯ３
モリブデン：（ＮＨ４）６Ｍｏ７Ｏ２４、和光純薬社製、９９．９９７％
ニオブ：ＮｂＣｌ５、Ａｌｆａ Ａｅｓａｒ社製、９９．９％
ナトリウム：Ｎａ２ＳＯ４、和光純薬製、９９．０＋％
イットリウム：Ｙ２（ＳＯ４）３、Ａｌｆａ Ａｅｓａｒ製、９９．９％Magnesium: ו 4 , made by Wako Pure Chemical Industries, Ltd., 98.0 +%
Beryllium: BeSO 4.nH 2 O, manufactured by Wako Pure Chemical Industries, Ltd., 50.0 +% (as anhydrous)
Tungsten: (NH 4 ) 10 W 12 O 4 , manufactured by Wako Pure Chemical Industries, Ltd., 85.0 +% as WO 3
Molybdenum: (NH 4 ) 6 Mo 7 O 24 , manufactured by Wako Pure Chemical Industries, Ltd., 99.997%
Niobium: NbCl 5 , manufactured by Alfa Aesar, 99.9%
Sodium: Na 2 SO 4 , manufactured by Wako Pure Chemical Industries, Ltd., 99.0 +%
Yttrium: Y 2 (SO 4 ) 3 , Alfa Aesar, 99.9%
〈分散液１１０の調製〉
酸化硫酸バナジウム（ＶＯＳＯ４）１９．０ｇをイオン交換水に溶解して３００ｍＬとし、この液を撹拌しながら、元素Ａとしてマグネシウム５．００ａｔｏｍ％（ＭｇＳＯ４、和光純薬製、９８．０＋％）、元素Ｂとしてタングステン１．００ａｔｏｍ％（（ＮＨ４）１０Ｗ１２Ｏ４、和光純薬社製、８５．０＋％ ａｓ ＷＯ３）及びモリブデン５．００ａｔｏｍ％（（ＮＨ４）６Ｍｏ７Ｏ２４、和光純薬社製、９９．９９７％）、アルカリとして３．０ｍｏｌ／ＬのＮＨ３水溶液を６８ｇ添加してｐＨを８．０（液温２５℃）として、反応液を調製した。
この反応液を内容積が５００ｍＬのオートクレーブに入れ、２７０℃、５．５１ＭＰａで２４時間、水熱反応させ、二酸化バナジウム含有粒子を含む分散液１１０を調製した。<Preparation of
Dissolve 19.0 g of vanadium oxide sulfate (VOSO 4 ) in ion-exchanged water to make 300 mL, and while stirring this solution, magnesium 5.00 atom% (trimethyl 4 , manufactured by Wako Pure Chemical Industries, 98.0 +%) as element A. , Tungsten 1.00 atom% ((NH 4 ) 10 W 12 O 4 , manufactured by Wako Pure Chemical Industries, Ltd., 85.0 +% as WO 3 ) and molybdenum 5.00 atom% ((NH 4 ) 6 Mo 7 O 24 ) as element B , Wako Junyaku Co., Ltd., 99.997%), 68 g of an NH3 aqueous solution of 3.0 mol / L as an alkali was added to adjust the pH to 8.0 (liquid temperature 25 ° C.) to prepare a reaction solution.
This reaction solution was placed in an autoclave having an internal volume of 500 mL and subjected to a hydrothermal reaction at 270 ° C. and 5.51 MPa for 24 hours to prepare a
〈分散液１１１の調製〉
分散液１０１の調製において、元素Ａ及び元素Ｂの種類及び添加量を表Ｉに記載のとおりに変更した以外は同様にして、分散液１１１を調製した。<Preparation of
In the preparation of the
〈分散液１１２～１２４の調製〉
分散液１１０の調製において、元素Ａ及び元素Ｂの種類及び添加量を表Ｉ及びIIに記載のとおりに変更した以外は同様にして、分散液１１２～１２４を調製した。
分散液１２４の調製に用いた、ニオブを含む化合物は、下記のとおりである。<Preparation of dispersions 112-124>
In the preparation of the
The compounds containing niobium used in the preparation of the dispersion liquid 124 are as follows.
ニオブ：ＮｂＣｌ５、Ａｌｆａ Ａｅｓａｒ社製、９９．９％Niobium: NbCl 5 , manufactured by Alfa Aesar, 99.9%
〈分散液１２５の調製〉
図１に記載の水熱反応部１１６を有する流通式反応装置１０１を用い、下記の方法に従って、二酸化バナジウム含有粒子を含む分散液１２５を調製した。<Preparation of dispersion liquid 125>
A dispersion liquid 125 containing vanadium dioxide-containing particles was prepared according to the following method using the flow-
まず、原料液容器１０５に、酸化硫酸バナジウム(IV)（ＶＯＳＯ４）１９．０ｇをイオン交換水（溶存酸素量：８．１ｍｇ／Ｌ）に溶解して３００ｍＬとし、この液を撹拌しながら、元素Ａとしてマグネシウム５．００ａｔｏｍ％（ＭｇＳＯ４、和光純薬製、９８．０＋％）、元素Ｂとしてタングステン１．００ａｔｏｍ％（（ＮＨ４）１０Ｗ１２Ｏ４、和光純薬社製、８５．０＋％ ａｓ ＷＯ３）及びモリブデン５．００ａｔｏｍ％（（ＮＨ４）６Ｍｏ７Ｏ２４、和光純薬社製、９９．９９７％）、アルカリとして３．０ｍｏｌ／ＬのＮＨ３水溶液を６８ｍＬ添加して、ｐＨが８．０（液温２５℃）の原料液１を調製した。
一方、原料液容器１０２にはイオン交換水を原料液２として収納した。First, 19.0 g of vanadium oxide sulfate (IV) (VOSO 4 ) was dissolved in ion-exchanged water (dissolved oxygen amount: 8.1 mg / L) to make 300 mL in the raw material
On the other hand, ion-exchanged water was stored as the raw material liquid 2 in the raw material
酸化硫酸バナジウム(IV)、元素Ａ、元素Ｂ及びアルカリを含む原料液１は、原料液容器１０５から流路１０６内をポンプ１０７により送液し、加熱媒体１１５で、２５℃で、３０ＭＰａの条件となるように加圧した。
一方、原料液２であるイオン交換水は、原料液容器１０２から流路１０３内をポンプ１０４により送液し、加熱媒体１１３で、４４０℃で、３０ＭＰａの条件で加熱加圧して、超臨界水を得た。The raw material liquid 1 containing vanadium (IV) oxide sulfate, element A, element B, and alkali is sent from the raw material
On the other hand, the ion-exchanged water, which is the raw material liquid 2, is sent from the raw material
次いで、合流点ＭＰで酸化硫酸バナジウム(IV)、元素Ａ、元素Ｂ及びアルカリを含む原料液１と、超臨界水である原料液２とを、体積比として原料液１：原料液２＝１：４となる条件で混合して、反応液１を調製し、水熱反応部１１６に送液した。水熱反応部１１６では、反応液１を加熱媒体１１４内に配置されている加熱部配管１１７に送液した。加熱配管部１１７における水熱反応条件としては、４５０℃、３０ＭＰａの条件で、処理時間（通過時間）を１分間となる条件で行い、二酸化バナジウム（ＶＯ２）含有粒子を形成した。次いで、冷却部１０８にて反応液１を冷却し、二酸化バナジウム含有粒子を含む分散液１２５を調製した。Next, the raw material liquid 1 containing vanadium oxide sulfate (IV), element A, element B and alkali at the confluence point MP and the raw material liquid 2 which is supercritical water are used as a volume ratio of raw material liquid 1: raw material liquid 2 = 1. The reaction solution 1 was prepared by mixing under the condition of: 4, and was sent to the
〈分散液１２６の調製〉
分散液１１０の調製において、水熱反応における処理温度及び圧力を２５０℃、３．９８ＭＰａに変更した以外は同様にして、二酸化バナジウム含有粒子を含む分散液１２６を調製した。<Preparation of dispersion 126>
In the preparation of the
〈分散液１２７の調製〉
分散液１２５の調製において、水熱反応における処理温度及び圧力を４８０℃、３０ＭＰａに変更した以外は同様にして、二酸化バナジウム含有粒子を含む分散液１２７を調製した。<Preparation of dispersion 127>
In the preparation of the dispersion liquid 125, the dispersion liquid 127 containing vanadium dioxide-containing particles was prepared in the same manner except that the treatment temperature and pressure in the hydrothermal reaction were changed to 480 ° C. and 30 MPa.
〈分散液１２８の調製〉
分散液１１０の調製において、水熱反応における処理温度及び圧力を２３０℃、２．８０ＭＰａに変更した以外は同様にして、二酸化バナジウム含有粒子を含む分散液１２８を調製した。<Preparation of dispersion 128>
In the preparation of the
〈分散液１２９の調製〉
分散液１１０の調製において、水熱反応における処理時間を４８時間に変更した以外は同様にして、二酸化バナジウム含有粒子を含む分散液１２９を調製した。<Preparation of dispersion liquid 129>
In the preparation of the
〈分散液１３０の調製〉
分散液１２５の調製において、水熱反応における処理温度及び圧力を２７０℃、５．５１ＭＰａ、処理時間（通過時間）を１秒間に変更した以外は同様にして、二酸化バナジウム含有粒子を含む分散液１３０を調製した。<Preparation of dispersion liquid 130>
In the preparation of the dispersion liquid 125, the treatment temperature and pressure in the hydrothermal reaction were changed to 270 ° C., 5.51 MPa, and the treatment time (passing time) was changed to 1 second. Was prepared.
〈分散液１３１の調製〉
分散液１１０の調製において、水熱反応における処理時間を１２０時間に変更した以外は同様にして、二酸化バナジウム含有粒子を含む分散液１３１を調製した。<Preparation of dispersion 131>
In the preparation of the
〈分散液１３２の調製〉
分散液１２５の調製において、水熱反応における処理温度及び圧力を２７０℃、５．５１ＭＰａ、処理時間（通過時間）を０．３秒間に変更した以外は同様にして、二酸化バナジウム含有粒子を含む分散液１３２を調製した。<Preparation of dispersion 132>
In the preparation of the dispersion liquid 125, the dispersion containing vanadium dioxide-containing particles was similarly changed except that the treatment temperature and pressure in the hydrothermal reaction were changed to 270 ° C. and 5.51 MPa, and the treatment time (passing time) was changed to 0.3 seconds. Liquid 132 was prepared.
〈分散液１３３～１３５の調製〉
分散液１２５の調製において、水熱反応における処理温度及び圧力を３５０℃、１６．５５ＭＰａ、及び元素Ａとしてのマグネシウムの添加量を表IIに記載のとおりに変更した以外は同様にして、分散液１３３～１３５を調製した。<Preparation of dispersions 133-135>
In the preparation of the dispersion liquid 125, the treatment temperature and pressure in the hydrothermal reaction were changed to 350 ° C., 16.55 MPa, and the amount of magnesium added as the element A was changed as shown in Table II. 133-135 were prepared.
《評価》
調製した分散液１０１～１３５について、下記評価を行った。
評価結果を表Ｉ及びIIに示す。"evaluation"
The
The evaluation results are shown in Tables I and II.
〈サーモクロミック性（ＴＣ性）〉
調製した各分散液を、二酸化バナジウム含有粒子を５質量％含む水分散液２０ｇに調製し、水９０ｇに溶解したポリビニルアルコール１０ｇ中に混合した。この混合液をＰＥＴフィルム上に塗布し、乾燥後の厚さが２０μｍになるようにワイヤーバーで塗布を行った後、６０℃で２４時間乾燥して測定用フィルムを作製した。測定用フィルム中の二酸化バナジウム含有粒子の濃度は１質量％であり、厚さは２０μｍであった。
作製した各測定用フィルムを用いて、１５℃及び７０℃の各条件における波長１０００ｎｍ、１１００ｎｍ及び１２００ｎｍでの光透過率を測定し、各波長での１５℃及び７０℃における光透過率の差を算出し、それらを加算した値について下記評価基準に従って評価した。なお、光透過率差の加算値が８０％以上であるものを合格とした。
光透過率の測定は、分光光度計Ｖ－６７０（日本分光（株）製）に温調ユニット（日本分光（株）製）を取り付けて行った。<Thermochromic (TC)>
Each of the prepared dispersions was prepared in 20 g of an aqueous dispersion containing 5% by mass of vanadium dioxide-containing particles, and mixed in 10 g of polyvinyl alcohol dissolved in 90 g of water. This mixed solution was applied onto a PET film, applied with a wire bar so that the thickness after drying was 20 μm, and then dried at 60 ° C. for 24 hours to prepare a measuring film. The concentration of the vanadium dioxide-containing particles in the measuring film was 1% by mass, and the thickness was 20 μm.
Using each of the produced measuring films, the light transmittance at wavelengths of 1000 nm and 1100 nm and 1200 nm under each condition of 15 ° C. and 70 ° C. was measured, and the difference in light transmittance at 15 ° C. and 70 ° C. at each wavelength was measured. It was calculated and the value obtained by adding them was evaluated according to the following evaluation criteria. Those in which the added value of the light transmittance difference was 80% or more were regarded as acceptable.
The light transmittance was measured by attaching a temperature control unit (manufactured by JASCO Corporation) to a spectrophotometer V-670 (manufactured by JASCO Corporation).
◎：１００％以上
○：９０％以上、１００％未満
△：８０％以上、９０％未満
×：８０％未満⊚: 100% or more ○: 90% or more, less than 100% Δ: 80% or more, less than 90% ×: less than 80%
〈色差〉
上記サーモクロミック性の評価における測定データを元に、ＪＩＳ Ｚ ８７８１－４：２０１３に準拠して、フィルム温度１５℃から７０℃への温度変化に伴う色差ΔＥ＊ａｂを算出し、下記評価基準に従って評価した。なお、色差ΔＥ＊ａｂが４以上であるものを合格とした。<Color difference>
Based on the measurement data in the evaluation of thermochromicity, the color difference ΔE * ab due to the temperature change from the film temperature of 15 ° C to 70 ° C was calculated according to JIS Z 8781-4: 2013, and according to the following evaluation criteria. evaluated. Those having a color difference ΔE * ab of 4 or more were regarded as acceptable.
◎：６以上
○：５以上、６未満
△：４以上、５未満
×：４未満⊚: 6 or more ○: 5 or more, less than 6 △: 4 or more and less than 5 ×: less than 4
〈まとめ〉
表Ｉ及びIIから明らかなように、本発明の二酸化バナジウム含有粒子を含む分散液は、比較例の分散液と比べて、サーモクロミック性及び色差において優れていることが確認された。
以上から、元素周期表の２族から選ばれる元素Ａと、バナジウムを除く元素周期表の５族又は６族から選ばれる元素Ｂとが含有され、バナジウム（１００ａｔｏｍ％）に対し、元素Ａの総含有量が０．５～２０ａｔｏｍ％の範囲内であり、かつ、元素Ｂの総含有量が０．０５～２０ａｔｏｍ％の範囲内であることが、可視光領域において温度変化により光透過率を変化させるとともに、赤外領域において温度変化による光透過率の変化幅をより増加させる二酸化バナジウム含有粒子を提供することに有用であることがわかる。<summary>
As is clear from Tables I and II, it was confirmed that the dispersion liquid containing the vanadium dioxide-containing particles of the present invention was superior in thermochromic property and color difference as compared with the dispersion liquid of the comparative example.
From the above, element A selected from Group 2 of the Periodic Table of the Elements and element B selected from Group 5 or Group 6 of the Periodic Table of the Elements excluding vanadium are contained, and the total amount of Element A is relative to vanadium (100 atom%). When the content is in the range of 0.5 to 20 atom% and the total content of element B is in the range of 0.05 to 20 atom%, the light transmission rate changes due to the temperature change in the visible light region. It can be seen that it is useful for providing vanadium dioxide-containing particles that further increase the range of change in light transmittance due to temperature changes in the infrared region.
本発明は、可視光領域において温度変化により光透過率を変化させるとともに、赤外光領域において温度変化による光透過率の変化幅をより増加させる二酸化バナジウム含有粒子、サーモクロミックフィルム及び二酸化バナジウム含有粒子の製造方法を提供することに、特に好適に利用することができる。 The present invention is a vanadium dioxide-containing particle, a thermochromic film, and a vanadium dioxide-containing particle that change the light transmittance due to a temperature change in the visible light region and further increase the change width of the light transmittance due to the temperature change in the infrared light region. It can be particularly preferably used to provide a method for producing the above.
１０１ 流通式反応装置
１０２、１０５ 原料液容器
１０３、１０６、１１１、１１８ 流路（配管）
１０４、１０７、１１２ ポンプ
１０８ 冷却部
１０９、１１０ タンク
１１３、１１４、１１５ 加熱媒体
１１６ 水熱反応部
１１７ 加熱部配管
１１９ 制御弁
Ｃ 冷媒
ＩＮ 加熱媒体の入口
ＯＵＴ 加熱媒体の出口
Ｌ 加熱部配管のライン長
ＭＰ 合流点
ＴＣ 温度センサー101
104, 107, 112
Claims (5)
元素Ａとしてマグネシウム又はベリリウムを含有し、元素Ｂとしてタングステン及びモリブデンを含有し、
バナジウム（１００ａｔｏｍ％）に対し、前記元素Ａの総含有量が０．５～２０ａｔｏｍ％の範囲内であり、かつ、前記元素Ｂの総含有量が０．０５～２０ａｔｏｍ％の範囲内であることを特徴とする二酸化バナジウム含有粒子。 Vanadium dioxide-containing particles with thermochromic properties.
It contains magnesium or beryllium as element A and tungsten and molybdenum as element B.
The total content of the element A is in the range of 0.5 to 20 atom% with respect to vanadium (100 atom%), and the total content of the element B is in the range of 0.05 to 20 atom%. Vanadium dioxide-containing particles characterized by.
前記１５℃から７０℃への温度変化に伴う色差ΔＥ＊ａｂが、下記式（１）を満たすことを特徴とする請求項２に記載のサーモクロミックフィルム。
４．０≦ΔＥ＊ａｂ≦６．５・・・（１） The light transmittance at wavelengths of 1000 nm and 1100 nm and 1200 nm at 15 ° C. and 70 ° C. was measured, the difference in light transmittance at 15 ° C. and 70 ° C. at each wavelength was calculated, and the light transmittance obtained by adding them together. The added value of the difference is 80% or more, and
The thermochromic film according to claim 2 , wherein the color difference ΔE * ab accompanying the temperature change from 15 ° C. to 70 ° C. satisfies the following formula (1).
4.0 ≤ ΔE * ab ≤ 6.5 ... (1)
バナジウム含有化合物と、元素Ａとしてマグネシウム又はベリリウムを、元素Ｂとしてタングステン及びモリブデンを含有し、更に水を含有する反応液を調製する工程と、
前記反応液を水熱反応させて、二酸化バナジウム含有粒子を形成する工程と、
を有し、
前記反応液を調製する工程では、バナジウム（１００ａｔｏｍ％）に対し、前記元素Ａの総添加量を０．５～２０ａｔｏｍ％の範囲内とし、かつ、前記元素Ｂの総添加量を０．０５～２０ａｔｏｍ％の範囲内とし、
二酸化バナジウム含有粒子を形成する工程では、液温２５０～４５０℃の範囲内、かつ、反応時間１秒～４８時間の範囲内で水熱反応させることを特徴とする二酸化バナジウム含有粒子の製造方法。 A method for producing vanadium dioxide-containing particles having thermochromic properties.
A step of preparing a reaction solution containing a vanadium-containing compound, magnesium or beryllium as the element A, tungsten and molybdenum as the element B, and further containing water.
A step of subjecting the reaction solution to a hydrothermal reaction to form vanadium dioxide-containing particles,
Have,
In the step of preparing the reaction solution, the total amount of the element A added is in the range of 0.5 to 20 atom% with respect to vanadium (100 atom%), and the total amount of the element B added is 0.05 to 0. Within the range of 20 atom%
In the step of forming the vanadium dioxide-containing particles, a method for producing vanadium dioxide-containing particles, which comprises a hydrothermal reaction within a liquid temperature range of 250 to 450 ° C. and a reaction time of 1 second to 48 hours. ..
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| US20120188628A1 (en) | 2011-01-25 | 2012-07-26 | Hon Hai Precision Industry Co., Ltd. | Coated article and method for making the same |
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| WO2016152879A1 (en) | 2015-03-24 | 2016-09-29 | コニカミノルタ株式会社 | Thermochromic film |
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| US20110260123A1 (en) | 2008-09-30 | 2011-10-27 | Granqvist Claes Goeran | Thermochromic material and fabrication method |
| JP2012149201A (en) | 2011-01-21 | 2012-08-09 | Sumitomo Metal Mining Co Ltd | Thermochromic body and method of producing the same |
| US20120188628A1 (en) | 2011-01-25 | 2012-07-26 | Hon Hai Precision Industry Co., Ltd. | Coated article and method for making the same |
| US20130342888A1 (en) | 2012-02-22 | 2013-12-26 | Kilolambda Technologies Ltd. | Responsivity Enhancement of Solar Light Compositions and Devices for Thermochromic Windows |
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