WO2017086376A1 - Method for producing vanadium dioxide-containing particles - Google Patents

Method for producing vanadium dioxide-containing particles Download PDF

Info

Publication number
WO2017086376A1
WO2017086376A1 PCT/JP2016/084062 JP2016084062W WO2017086376A1 WO 2017086376 A1 WO2017086376 A1 WO 2017086376A1 JP 2016084062 W JP2016084062 W JP 2016084062W WO 2017086376 A1 WO2017086376 A1 WO 2017086376A1
Authority
WO
WIPO (PCT)
Prior art keywords
vanadium dioxide
containing particles
particles
particle size
hydrothermal reaction
Prior art date
Application number
PCT/JP2016/084062
Other languages
French (fr)
Japanese (ja)
Inventor
貴志 鷲巣
Original Assignee
コニカミノルタ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to CN201680066573.1A priority Critical patent/CN108349745B/en
Priority to JP2017551918A priority patent/JPWO2017086376A1/en
Publication of WO2017086376A1 publication Critical patent/WO2017086376A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy

Definitions

  • the present invention relates to a method for producing vanadium dioxide-containing particles, and more particularly to a method for producing vanadium dioxide-containing particles having excellent thermochromic properties and storage stability.
  • Vanadium dioxide (VO 2 ) particles have attracted attention as a material exhibiting a thermochromic phenomenon in which optical characteristics such as light transmittance and light reflectance change reversibly with temperature changes.
  • rutile-type crystal phase 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 (referred to as so-called “rutile-type crystal phase”).
  • 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.
  • the particle size is on the order of nanometers, there is no aggregation, and the particle size distribution is narrow.
  • a hydrothermal synthesis method has been reported as a technique for producing such particles (see, for example, Patent Document 1). According to the hydrothermal synthesis method, it is possible to produce particles having a particle size of the order of nanometers. However, when vanadium dioxide particles are used for window films or the like, the vanadium dioxide particles need to have a particle size of 40 nm or less in order to prevent the occurrence of haze, but such vanadium dioxide particles are produced only by the hydrothermal synthesis method. Is not enough. In addition, it is difficult to synthesize vanadium dioxide particles having a uniform particle size, and particles having a particle size of 40 nm or more are mixed. Filtration or the like can be considered as a means for removing particles having a large particle diameter mixed in this way. However, particles having a particle diameter of about 200 nm are clogged during filtration and are difficult to remove.
  • Patent Document 2 As a method for obtaining vanadium dioxide particles having a smaller particle diameter, it is conceivable to crush vanadium dioxide particles (for example, see Patent Document 2).
  • Patent Document 2 introduces a crushing method and conditions using a bead mill. However, when a large particle size is crushed, many defective sites are generated in the crystal structure, resulting in decreased thermochromic properties and storage stability. Resulting in.
  • the present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is to provide a method for producing vanadium dioxide-containing particles having excellent thermochromic properties and storage stability.
  • the present inventor has a process of forming vanadium dioxide-containing particles by hydrothermal reaction and a process of crushing vanadium dioxide-containing particles by a hydrothermal reaction.
  • the vanadium dioxide-containing particles having excellent thermochromic properties and storage stability can be provided by setting the particle size of the vanadium dioxide-containing particles of 80% by number or more to 50 nm or less.
  • the headline, the present invention has been reached.
  • a method for producing vanadium dioxide-containing particles having thermochromic properties Forming vanadium dioxide-containing particles by a hydrothermal reaction; Crushing the vanadium dioxide-containing particles; Have In the step of crushing the vanadium dioxide-containing particles, the particle size of the vanadium dioxide-containing particles of 80% by number or more is set to 50 nm or less.
  • the vanadium dioxide-containing particles according to claim 1 wherein the vanadium dioxide-containing particles having a particle diameter of 100 nm or less are formed by hydrothermal reaction to form 70% by number or more. Production method.
  • the hydrothermal reaction is performed at 230 ° C. or higher, and the time until the reaction system reaches from 25 ° C. to 200 ° C. is within one hour.
  • the above-mentioned means of the present invention can provide a method for producing vanadium dioxide-containing particles having excellent thermochromic properties and storage stability.
  • the method for producing vanadium dioxide-containing particles according to the present invention is characterized in that after the vanadium dioxide-containing particles are formed by a hydrothermal reaction, the particle size of the vanadium dioxide-containing particles of 80% by number or more is crushed so as to be 50 nm or less. Yes.
  • particles having a large particle size are mixed, but as described above, by crushing the particles synthesized by the hydrothermal reaction, the target particles are minimized while minimizing the defect site. Particles containing vanadium dioxide having a diameter can be obtained.
  • particles synthesized by hydrothermal reaction are slightly lower in crystallinity than particles produced by a baking method, etc., and are easily crushed. It is done.
  • the vanadium dioxide-containing particles produced by the method for producing vanadium dioxide-containing particles of the present invention have a particle size of 80% by number or more and 50 nm or less.
  • the haze value is small and the defect site is kept to a minimum, it is presumed that the thermochromic property and the storage stability of the thermochromic property can be maintained.
  • thermochromic vanadium dioxide-containing particles of the present invention comprises a step of forming vanadium dioxide-containing particles by a hydrothermal reaction, and a step of crushing vanadium dioxide-containing particles, and the vanadium dioxide-containing particles In the step of crushing, the particle size of the vanadium dioxide-containing particles of 80% by number or more is 50 nm or less. This feature is a technical feature common to the claimed invention.
  • part can be minimized more and thermochromic property and its storage stability can be maintained.
  • vanadium dioxide-containing particles that exhibit thermochromic properties
  • at least the vanadium compound, the reducing agent, and water are mixed and hydrothermally reacted in the step of forming the vanadium dioxide-containing particles.
  • the reducing agent is oxalic acid, formic acid, hydrazine, or a hydrate thereof from the viewpoint that 70% by number or more of vanadium dioxide-containing particles having a particle size of 100 nm or less can be stably produced. It is preferable that the hydrothermal reaction is performed at 230 ° C. or higher and the time until the reaction system reaches from 25 ° C. to 200 ° C. is within 1 hour.
  • ⁇ representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • the method for producing thermochromic vanadium dioxide-containing particles of the present invention comprises a step of forming vanadium dioxide-containing particles by a hydrothermal reaction, and a step of crushing vanadium dioxide-containing particles, and the vanadium dioxide-containing particles In the step of crushing, the particle size of the vanadium dioxide-containing particles of 80% by number or more is 50 nm or less.
  • the particle size of the vanadium dioxide-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.
  • ⁇ Hydrothermal reaction> it is preferable to synthesize vanadium dioxide-containing particles by mixing at least a vanadium compound, a reducing agent, and water and causing a hydrothermal reaction.
  • vanadium dioxide-containing particles having a rutile-type crystal structure R phase (M layer)
  • the hydrothermal reaction means a chemical reaction in which temperature and pressure are lower than the critical point of water (374 ° C., 22 MPa) and proceed in hot water (subcritical water) at 100 ° C. or higher.
  • the hydrothermal reaction is performed, for example, in a closed container such as an autoclave apparatus. At this time, hydrogen peroxide may be mixed.
  • the conditions of the hydrothermal reaction treatment are set as appropriate, but the liquid temperature of the hydrothermal reaction is, for example, in the range of 200 to 350 ° C. Is preferable, more preferably in the range of 200 to 300 ° C., and particularly preferably in the range of 230 to 300 ° C. If the liquid temperature is 200 ° C. or higher, a sufficient reaction rate can be obtained.
  • the hydrothermal reaction is carried out at 230 ° C. or higher, and the time until the reaction system reaches from 25 ° C. to 200 ° C. is preferably within 2 hours, more preferably within 1 hour. Thereby, the vanadium dioxide containing particle produced can be reduced in particle size.
  • the hydrothermal reaction time is, for example, 1 hour to 7 days. By increasing the time, it is possible to control the average particle size and the like of the obtained vanadium dioxide-containing particles, and when it is within 7 days, it is possible to suppress an excessive increase in energy consumption.
  • the hydrothermal reaction is performed with stirring because the particle diameter of the vanadium dioxide-containing particles can be made more uniform.
  • the hydrothermal reaction may be performed by either a batch method or a continuous method.
  • the hydrothermal reaction it is preferable to form 70% by number or more of vanadium dioxide-containing particles having a particle size of 100 nm or less.
  • the method for controlling the particle size of the vanadium dioxide-containing particles produced by the hydrothermal reaction can be controlled by appropriately selecting the temperature during the hydrothermal reaction, the temperature rising rate, and the like.
  • the particle size is greatly influenced by the temperature rising rate, and the temperature rising rate up to 200 ° C. can be controlled within 1 hour to control the desired particle size.
  • the reaction After completion of the reaction, it is preferable to quickly cool to 150 ° C. or lower. 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.
  • the vanadium dioxide-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.
  • Ultrafiltration As the 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).
  • the particle size of the vanadium dioxide-containing particles of 80% by number or more is 50 nm or less.
  • the method for crushing the vanadium dioxide-containing particles is not particularly limited, and can be performed using a device such as a high-speed stirrer, a high-pressure homogenizer, a bead mill, and a shaker. Among them, it is preferable to crush using a high-pressure homogenizer or a bead mill from the viewpoint of particle miniaturization.
  • a high-pressure homogenizer is a commercially available device that grinds by shearing force due to accelerated high flow velocity, rapid pressure drop (cavitation), and impact force caused by high-velocity particles colliding face-to-face within a fine orifice.
  • a nanomizer manufactured by Nanomizer Co., Ltd.
  • a microfluidizer manufactured by Microfluidics
  • the degree of crushing by the high-pressure homogenizer depends on the pressure fed to the high-pressure homogenizer and the number of passes through the high-pressure homogenizer (number of passes).
  • the bead mill has a step of filling a container with beads as a medium, pouring a slurry of particles and medium into the stirred beads, and crushing and pulverizing and dispersing the aggregated particles by stirring together with the beads in the medium.
  • Device There is also an apparatus that uses centrifugal separation to separate the slurry and beads.
  • Such a bead mill include Star Mill ZRS (manufactured by Ashizawa Finetech Co., Ltd.), Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.), and MSC-MILL (Mitsui Mining Co., Ltd.).
  • the beads used in the bead mill are not particularly limited, and examples thereof include metals and ceramics.
  • zirconia beads and alumina beads can be used.
  • the size of the beads is selected according to the purpose.
  • the particle size of the beads to be applied is preferably about 0.03 to 0.3 mm.
  • the crushing using a bead mill is preferably used such that the beads are in the range of 10 to 80% by volume in the container.
  • the treatment time in the bead mill is preferably about 10 minutes to 24 hours, and if the treatment is further performed, contamination from the beads may be mixed.
  • a dispersing agent can be added as needed during crushing.
  • Commercially available anionic surfactants, cationic surfactants, nonionic surfactants, metal alkoxides and the like can be preferably used.
  • the addition amount of the dispersant is preferably 40% by mass or less of the particle mass.
  • the vanadium dioxide-containing particles according to the present invention are configured to include at least vanadium dioxide, and thereby can exhibit thermochromic properties.
  • the thermochromic property of the vanadium dioxide-containing particles is not particularly limited as long as optical properties such as light transmittance and light reflectance change reversibly with temperature.
  • the light transmittance of the film to which the vanadium dioxide-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).
  • the light transmittance of the film to which the vanadium dioxide-containing particles are added is preferably as high as possible, but is preferably 70% or more.
  • the vanadium dioxide-containing particles according to the present invention are characterized in that a particle size of 80% by number or more is 50 nm or less. For this reason, even when the vanadium dioxide-containing particles according to the present invention are used mixed with a window film, the haze value is small, and since the defect site is minimized, the thermochromic property and its storage stability Sex can be maintained.
  • 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.
  • ⁇ Reducing agent Although it does not specifically limit as a reducing agent which concerns on this invention, It is preferable that they are oxalic acid, formic acid, hydrazine, or those hydrates.
  • the particle size distribution of the produced particles was measured using a laser diffraction particle size distribution meter. Specifically, the particles were mixed with water so as to have a concentration of 1% by mass, dispersed with ultrasonic waves for 15 minutes to prepare a sample, and measured using a laser diffraction particle size distribution analyzer manufactured by Shimadzu Corporation. .
  • Vanadium dioxide particles were prepared with reference to Example 1 of Japanese Patent No. 5625172.
  • the vanadium dioxide particles contained 32% by number of particles having a particle size of 100 nm or less.
  • the produced particles were subjected to bead milling to crush the particles.
  • particles and water were mixed to make 500 mL of a 10% by mass dispersion.
  • 200 g of zirconia beads having a particle diameter of 0.1 mm was mixed, and crushed for 20 minutes using an Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) to prepare Sample 101.
  • the particle diameter of 81% by number of vanadium dioxide-containing particles was 50 nm or less.
  • the prepared liquid mixture is put in a high-pressure reaction decomposition container stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample container HUTc-50: manufactured by Sanai Kagaku Co., Ltd.), and subjected to a hydrothermal reaction at 260 ° C. for 48 hours. went. At this time, the temperature raising time from 25 ° C. to 200 ° C. was 3 hours.
  • the vanadium dioxide-containing particles contained 31% by number of particles having a particle size of 100 nm or less.
  • the obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium dioxide-containing particles.
  • the prepared dispersion was subjected to bead milling to crush the particles.
  • the dispersion was concentrated to 500 mL of a 10% by mass dispersion.
  • 200 g of zirconia beads having a particle size of 0.1 mm was mixed with this dispersion, and crushing was performed for 15 minutes using an Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) to produce Sample 102.
  • the particle diameter of 73% by number of vanadium dioxide-containing particles was 50 nm or less.
  • Sample 103 was prepared in the same manner as in the preparation of sample 102, except that the crushing time by the bead mill was 20 minutes. In the sample 103 after crushing, the particle size of 82% by number of vanadium dioxide-containing particles was 50 nm or less.
  • Sample 104 was prepared in the same manner as in the preparation of Sample 103 except that the temperature raising time from 25 ° C. to 200 ° C. was set to 1 hour.
  • the vanadium dioxide-containing particles immediately after the hydrothermal reaction contained 72% by number of particles having a particle size of 100 nm or less. Further, in the sample 104 after crushing, the particle size of 81% by number of vanadium dioxide-containing particles was 50 nm or less.
  • Sample 105 was prepared in the same manner as in the preparation of sample 104 except that the crushing time by the bead mill was 45 minutes. In the sample 105 after crushing, the particle size of 92% by number of vanadium dioxide-containing particles was 50 nm or less.
  • Sample 106 was produced in the same manner as in the production of sample 105 except that the temperature raising time from 25 ° C. to 200 ° C. was changed to 45 minutes.
  • the vanadium dioxide-containing particles immediately after the hydrothermal reaction contained 81% by number of particles having a particle size of 100 nm or less.
  • the particle size of 91% by number of vanadium dioxide-containing particles was 50 nm or less.
  • Sample 107 was produced in the same manner as in the production of sample 105 except that the hydrothermal reaction was performed as follows.
  • V divanadium pentoxide
  • V 2 O 5 special grade, Wako Pure Chemical Industries
  • aqueous solution obtained by mixing 2 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 mL of pure water.
  • the prepared liquid mixture is put in a high-pressure reaction decomposition container stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample container HUTc-50: manufactured by Sanai Kagaku Co., Ltd.), and subjected to a hydrothermal reaction at 260 ° C. for 48 hours. went. At this time, the temperature raising time from 25 ° C. to 200 ° C. was set to 1 hour.
  • the vanadium dioxide-containing particles immediately after the hydrothermal reaction contained 71% by number of particles having a particle size of 100 nm or less. Further, in the sample 107 after crushing, the particle size of 91% by number of vanadium dioxide-containing particles was 50 nm or less.
  • Sample 108 was produced in the same manner as in the production of sample 105 except that the hydrothermal reaction was performed as follows.
  • V divanadium pentoxide
  • HCOOH formic acid
  • the prepared liquid mixture is put in a high-pressure reaction decomposition container stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample container HUTc-50: manufactured by Sanai Kagaku Co., Ltd.), and subjected to a hydrothermal reaction at 260 ° C. for 48 hours. went. At this time, the temperature raising time from 25 ° C. to 200 ° C. was set to 1 hour.
  • the vanadium dioxide-containing particles immediately after the hydrothermal reaction contained 72% by number of particles having a particle size of 100 nm or less.
  • the particle size of 92% by number of vanadium dioxide-containing particles was 50 nm or less.
  • thermochromic storage stability The light transmittance difference ( ⁇ T (%)) after storing each measurement film prepared above at 60 ° C./90% RH for 1000 hours was calculated in the same manner as the thermochromic evaluation, before and after storage.
  • Retention rate (%) ( ⁇ T (%) after storage) / ( ⁇ T (%) before storage) ⁇ 100
  • the samples 103 to 108 produced by the method for producing vanadium dioxide-containing particles of the present invention are superior in thermochromic properties and their storage stability compared to the samples 101 and 102 of the comparative examples. It is shown that.
  • sample 101 vanadium dioxide-containing particles before crushing are produced by firing instead of the hydrothermal method. Therefore, particle deterioration (defect site) due to crushing is large, and as a result, thermochromic properties and storage stability thereof are improved. It is falling.
  • the sample 102 shortens the crushing time, the deterioration due to crushing is small and the same storage stability as that of the sample 103 is obtained.
  • the step of crushing vanadium dioxide-containing particles contains 80% or more vanadium dioxide. It can be seen that the method for producing vanadium dioxide-containing particles having a particle size of 50 nm or less is useful for providing vanadium dioxide-containing particles having excellent thermochromic properties and storage stability.
  • the present invention can be particularly suitably used for providing a method for producing vanadium dioxide-containing particles having excellent thermochromic properties and storage stability.

Abstract

The present invention addresses the problem of providing a method for producing vanadium dioxide-containing particles which have excellent thermochromic properties and storage stability. This method for producing vanadium dioxide-containing particles is characterized by including: a step of forming the vanadium dioxide-containing particles by a hydrothermal reaction; and a step of fracturing the vanadium dioxide-containing particles wherein the particle size of 80 number% or more of the vanadium dioxide-containing particles is 50 nm or less.

Description

二酸化バナジウム含有粒子の製造方法Method for producing vanadium dioxide-containing particles
　本発明は、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、サーモクロミック性及び保存安定性に優れた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, and more particularly to a method for producing vanadium dioxide-containing particles having excellent thermochromic properties and storage stability.
　二酸化バナジウム（ＶＯ２）粒子は、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。
　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、粒径がナノメートルオーダーであり、凝集がなく、狭い粒径分布であることが望ましい。 Vanadium dioxide (VO 2 ) particles have attracted attention as a material exhibiting a thermochromic phenomenon in which optical characteristics such as light transmittance and light reflectance change reversibly with temperature changes.
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 (referred to as so-called “rutile-type crystal phase”). 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 develop substantially excellent thermochromic properties, it is desirable that the particle size is on the order of nanometers, there is no aggregation, and the particle size distribution is narrow.
　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。）。当該水熱合成法によれば、粒径がナノメートルオーダーの粒子を作製することが可能となる。
　しかしながら、二酸化バナジウム粒子をウィンドウフィルム等に用いる場合、ヘイズの発生を防ぐために二酸化バナジウム粒子の粒径を４０ｎｍ以下にする必要があるが、水熱合成法のみではこのような二酸化バナジウム粒子を作製するには不十分である。加えて、均一な粒径を有する二酸化バナジウム粒子を合成するのは困難であり、粒径４０ｎｍ以上の粒子が混在してしまう。
　このように混在してしまった粒径の大きい粒子を取り除く手段として濾過などが考えられるが、粒径２００ｎｍ程度の粒子は濾過時に目詰まりを起こしてしまい、取り除くことが困難である。 A hydrothermal synthesis method has been reported as a technique for producing such particles (see, for example, Patent Document 1). According to the hydrothermal synthesis method, it is possible to produce particles having a particle size of the order of nanometers.
However, when vanadium dioxide particles are used for window films or the like, the vanadium dioxide particles need to have a particle size of 40 nm or less in order to prevent the occurrence of haze, but such vanadium dioxide particles are produced only by the hydrothermal synthesis method. Is not enough. In addition, it is difficult to synthesize vanadium dioxide particles having a uniform particle size, and particles having a particle size of 40 nm or more are mixed.
Filtration or the like can be considered as a means for removing particles having a large particle diameter mixed in this way. However, particles having a particle diameter of about 200 nm are clogged during filtration and are difficult to remove.
　より粒径の小さい二酸化バナジウム粒子を得る方法として、二酸化バナジウム粒子を破砕することが考えられる（例えば、特許文献２参照。）。
　当該特許文献２には、ビーズミルを用いた破砕方法・条件が紹介されているが、粒径の大きい粒子を破砕すると結晶構造に多くの欠損部位が生じるため、サーモクロミック性や保存安定性が低下してしまう。 As a method for obtaining vanadium dioxide particles having a smaller particle diameter, it is conceivable to crush vanadium dioxide particles (for example, see Patent Document 2).
Patent Document 2 introduces a crushing method and conditions using a bead mill. However, when a large particle size is crushed, many defective sites are generated in the crystal structure, resulting in decreased thermochromic properties and storage stability. Resulting in.
特開２０１１－１７８８２５号公報JP 2011-178825 A 特開２０１２－２５０８７９号公報JP 2012-250879 A
　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保存安定性に優れた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-mentioned problems and situations, and the problem to be solved is to provide a method for producing vanadium dioxide-containing particles having excellent thermochromic properties and storage stability.
　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、水熱反応により、二酸化バナジウム含有粒子を形成する工程と、二酸化バナジウム含有粒子を破砕する工程と、を有し、二酸化バナジウム含有粒子を破砕する工程において、８０個数％以上の二酸化バナジウム含有粒子の粒径を５０ｎｍ以下とすることにより、サーモクロミック性及び保存安定性に優れた二酸化バナジウム含有粒子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 has a process of forming vanadium dioxide-containing particles by hydrothermal reaction and a process of crushing vanadium dioxide-containing particles by a hydrothermal reaction. In the step of crushing the vanadium dioxide-containing particles, the vanadium dioxide-containing particles having excellent thermochromic properties and storage stability can be provided by setting the particle size of the vanadium dioxide-containing particles of 80% by number or more to 50 nm or less. The headline, the present invention has been reached.
　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の製造方法であって、
　水熱反応により、二酸化バナジウム含有粒子を形成する工程と、
　前記二酸化バナジウム含有粒子を破砕する工程と、
を有し、
　前記二酸化バナジウム含有粒子を破砕する工程では、８０個数％以上の前記二酸化バナジウム含有粒子の粒径を５０ｎｍ以下とす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。 1. A method for producing vanadium dioxide-containing particles having thermochromic properties,
Forming vanadium dioxide-containing particles by a hydrothermal reaction;
Crushing the vanadium dioxide-containing particles;
Have
In the step of crushing the vanadium dioxide-containing particles, the particle size of the vanadium dioxide-containing particles of 80% by number or more is set to 50 nm or less.
　２．前記二酸化バナジウム含有粒子を形成する工程では、水熱反応により、粒径が１００ｎｍ以下である二酸化バナジウム含有粒子を７０個数％以上形成することを特徴とする第１項に記載の二酸化バナジウム含有粒子の製造方法。 2. In the step of forming the vanadium dioxide-containing particles, the vanadium dioxide-containing particles according to claim 1, wherein the vanadium dioxide-containing particles having a particle diameter of 100 nm or less are formed by hydrothermal reaction to form 70% by number or more. Production method.
　３．前記二酸化バナジウム含有粒子を形成する工程では、少なくとも、バナジウム化合物と還元剤と水とを混合して水熱反応させることを特徴とする第１項又は第２項に記載の二酸化バナジウム含有粒子の製造方法。 3. 3. The production of vanadium dioxide-containing particles according to claim 1 or 2, wherein in the step of forming the vanadium dioxide-containing particles, at least a vanadium compound, a reducing agent, and water are mixed and subjected to a hydrothermal reaction. Method.
　４．前記還元剤が、シュウ酸、ギ酸、ヒドラジン、又はそれらの水和物であることを特徴とする第３項に記載の二酸化バナジウム含有粒子の製造方法。 4. 4. The method for producing vanadium dioxide-containing particles according to item 3, wherein the reducing agent is oxalic acid, formic acid, hydrazine, or a hydrate thereof.
　５．前記二酸化バナジウム含有粒子を形成する工程では、２３０℃以上で水熱反応を行い、かつ、反応系が２５℃から２００℃に到達するまでの時間を１時間以内とす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二酸化バナジウム含有粒子の製造方法。 5. In the step of forming the vanadium dioxide-containing particles, the hydrothermal reaction is performed at 230 ° C. or higher, and the time until the reaction system reaches from 25 ° C. to 200 ° C. is within one hour. The manufacturing method of the vanadium dioxide containing particle | grains as described in any one of claim | item 4 -4.
　本発明の上記手段により、サーモクロミック性及び保存安定性に優れた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 above-mentioned means of the present invention can provide a method for producing vanadium dioxide-containing particles having excellent thermochromic properties and storage stability.
　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.
　本発明の二酸化バナジウム含有粒子の製造方法は、水熱反応により二酸化バナジウム含有粒子を形成した後、８０個数％以上の二酸化バナジウム含有粒子の粒径が５０ｎｍ以下となるように破砕することを特徴としている。
　特許文献１に記載の方法では粒径の大きい粒子が混在してしまうが、上記のように、水熱反応により合成した粒子を破砕することで、欠損部位を最小限にしつつ、目的とする粒径の二酸化バナジウム含有粒子を得ることができる。また、水熱反応で合成した粒子は、焼成法などで作製された粒子よりも結晶性がわずかに低く、破砕しやすいため、より少ない破砕処理で目的の粒径とすることができるものと考えられる。
　以上のように、本発明の二酸化バナジウム含有粒子の製造方法により作製された二酸化バナジウム含有粒子は８０個数％以上の粒径が５０ｎｍ以下であるため、ウィンドウフィルムに混合して使用した場合であってもヘイズ値が小さく、また、欠損部位を最小限にとどめているため、サーモクロミック性と、サーモクロミック性の保存安定性も維持できているものと推察される。 The method for producing vanadium dioxide-containing particles according to the present invention is characterized in that after the vanadium dioxide-containing particles are formed by a hydrothermal reaction, the particle size of the vanadium dioxide-containing particles of 80% by number or more is crushed so as to be 50 nm or less. Yes.
In the method described in Patent Document 1, particles having a large particle size are mixed, but as described above, by crushing the particles synthesized by the hydrothermal reaction, the target particles are minimized while minimizing the defect site. Particles containing vanadium dioxide having a diameter can be obtained. In addition, particles synthesized by hydrothermal reaction are slightly lower in crystallinity than particles produced by a baking method, etc., and are easily crushed. It is done.
As described above, the vanadium dioxide-containing particles produced by the method for producing vanadium dioxide-containing particles of the present invention have a particle size of 80% by number or more and 50 nm or less. However, since the haze value is small and the defect site is kept to a minimum, it is presumed that the thermochromic property and the storage stability of the thermochromic property can be maintained.
　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は、水熱反応により、二酸化バナジウム含有粒子を形成する工程と、二酸化バナジウム含有粒子を破砕する工程と、を有し、二酸化バナジウム含有粒子を破砕する工程では、８０個数％以上の二酸化バナジウム含有粒子の粒径を５０ｎｍ以下とす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 method for producing thermochromic vanadium dioxide-containing particles of the present invention comprises a step of forming vanadium dioxide-containing particles by a hydrothermal reaction, and a step of crushing vanadium dioxide-containing particles, and the vanadium dioxide-containing particles In the step of crushing, the particle size of the vanadium dioxide-containing particles of 80% by number or more is 50 nm or less. This feature is a technical feature common to the claimed invention.
　本発明の実施態様としては、二酸化バナジウム含有粒子を形成する工程において、水熱反応により、粒径が１００ｎｍ以下である二酸化バナジウム含有粒子を７０個数％以上形成することが好ましい。これにより、より欠損部位を最小限にし、サーモクロミック性とその保存安定性も維持することができる。 As an embodiment of the present invention, it is preferable to form 70% by number or more of vanadium dioxide-containing particles having a particle size of 100 nm or less by a hydrothermal reaction in the step of forming vanadium dioxide-containing particles. Thereby, a defect site | part can be minimized more and thermochromic property and its storage stability can be maintained.
　また、サーモクロミック性を発現する二酸化バナジウム含有粒子を得る観点から、二酸化バナジウム含有粒子を形成する工程では、少なくとも、バナジウム化合物と還元剤と水とを混合して水熱反応させることが好ましい。 Further, from the viewpoint of obtaining vanadium dioxide-containing particles that exhibit thermochromic properties, it is preferable that at least the vanadium compound, the reducing agent, and water are mixed and hydrothermally reacted in the step of forming the vanadium dioxide-containing particles.
　また、粒径が１００ｎｍ以下である二酸化バナジウム含有粒子を７０個数％以上安定して製造できる点から、還元剤がシュウ酸、ギ酸、ヒドラジン、又はそれらの水和物であることが好ましく、更には、２３０℃以上で水熱反応を行い、かつ、反応系が２５℃から２００℃に到達するまでの時間を１時間以内とすることが好ましい。 Moreover, it is preferable that the reducing agent is oxalic acid, formic acid, hydrazine, or a hydrate thereof from the viewpoint that 70% by number or more of vanadium dioxide-containing particles having a particle size of 100 nm or less can be stably produced. It is preferable that the hydrothermal reaction is performed at 230 ° C. or higher and the time until the reaction system reaches from 25 ° C. to 200 ° C. is within 1 hour.
　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 the present application, “˜” representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
《二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二酸化バナジウム含有粒子の製造方法は、水熱反応により、二酸化バナジウム含有粒子を形成する工程と、二酸化バナジウム含有粒子を破砕する工程と、を有し、二酸化バナジウム含有粒子を破砕する工程では、８０個数％以上の二酸化バナジウム含有粒子の粒径を５０ｎｍ以下とすることを特徴とする。
　なお、本発明において、二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。 << Method for producing vanadium dioxide-containing particles >>
The method for producing thermochromic vanadium dioxide-containing particles of the present invention comprises a step of forming vanadium dioxide-containing particles by a hydrothermal reaction, and a step of crushing vanadium dioxide-containing particles, and the vanadium dioxide-containing particles In the step of crushing, the particle size of the vanadium dioxide-containing particles of 80% by number or more is 50 nm or less.
In the present invention, the particle size of the vanadium dioxide-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.
〈水熱反応〉
　本発明においては、少なくとも、バナジウム化合物と還元剤と水とを混合して水熱反応させることにより、二酸化バナジウム含有粒子を合成することが好ましい。バナジウム化合物を水熱反応下で還元することで、ルチル型の結晶構造（Ｒ相（Ｍ層））を有する二酸化バナジウム含有粒子を作製することができる。 <Hydrothermal reaction>
In the present invention, it is preferable to synthesize vanadium dioxide-containing particles by mixing at least a vanadium compound, a reducing agent, and water and causing a hydrothermal reaction. By reducing the vanadium compound under a hydrothermal reaction, vanadium dioxide-containing particles having a rutile-type crystal structure (R phase (M layer)) can be produced.
　本発明において、水熱反応とは、温度と圧力が水の臨界点（３７４℃、２２ＭＰａ）よりも低く、１００℃以上の熱水（亜臨界水）中において進行する化学反応を意味する。水熱反応は、例えば、オートクレーブ装置等の密閉容器内で実施される。このとき、過酸化水素を混合していてもよい。 In the present invention, the hydrothermal reaction means a chemical reaction in which temperature and pressure are lower than the critical point of water (374 ° C., 22 MPa) and proceed in hot water (subcritical water) at 100 ° C. or higher. The hydrothermal reaction is performed, for example, in a closed container such as an autoclave apparatus. At this time, hydrogen peroxide may be mixed.
　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、水熱反応の液温としては、例えば、２００～３５０℃の範囲内であることが好ましく、２００～３００℃の範囲内であることがより好ましく、２３０～３００℃の範囲内であることが特に好ましい。液温が２００℃以上であれば十分な反応速度が得られる。
　また、本発明においては、２３０℃以上で水熱反応を行い、かつ、反応系が２５℃から２００℃に到達するまでの時間を２時間以内、より好ましくは１時間以内とすることが好ましい。これにより、作製される二酸化バナジウム含有粒子を小粒径化することができる。 The conditions of the hydrothermal reaction treatment (reaction amount, treatment temperature, treatment pressure, treatment time) are set as appropriate, but the liquid temperature of the hydrothermal reaction is, for example, in the range of 200 to 350 ° C. Is preferable, more preferably in the range of 200 to 300 ° C., and particularly preferably in the range of 230 to 300 ° C. If the liquid temperature is 200 ° C. or higher, a sufficient reaction rate can be obtained.
In the present invention, the hydrothermal reaction is carried out at 230 ° C. or higher, and the time until the reaction system reaches from 25 ° C. to 200 ° C. is preferably within 2 hours, more preferably within 1 hour. Thereby, the vanadium dioxide containing particle produced can be reduced in particle size.
　また、水熱反応時間は、例えば、１時間～７日である。時間を長くすることにより、得られる二酸化バナジウム含有粒子の平均粒径等を制御することができ、７日以内であると、エネルギー消費量が多くなりすぎることを抑制できる。 The hydrothermal reaction time is, for example, 1 hour to 7 days. By increasing the time, it is possible to control the average particle size and the like of the obtained vanadium dioxide-containing particles, and when it is within 7 days, it is possible to suppress an excessive increase in energy consumption.
　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。 In addition, it is preferable that the hydrothermal reaction is performed with stirring because the particle diameter of the vanadium dioxide-containing particles can be made more uniform.
　水熱反応は、バッチ式又は連続式のいずれの方法で実施してもよい。 The hydrothermal reaction may be performed by either a batch method or a continuous method.
　また、水熱反応では、粒径が１００ｎｍ以下である二酸化バナジウム含有粒子を７０個数％以上形成することが好ましい。
　水熱反応により作製される二酸化バナジウム含有粒子の粒径を制御する方法としては、水熱反応時の温度、昇温速度等を適宜選択することにより制御することができる。特に、粒径には昇温速度の影響が大きく、２００℃までの昇温速度を１時間以内とすることで所望の粒径に制御することが可能となる。 In the hydrothermal reaction, it is preferable to form 70% by number or more of vanadium dioxide-containing particles having a particle size of 100 nm or less.
The method for controlling the particle size of the vanadium dioxide-containing particles produced by the hydrothermal reaction can be controlled by appropriately selecting the temperature during the hydrothermal reaction, the temperature rising rate, and the like. In particular, the particle size is greatly influenced by the temperature rising rate, and the temperature rising rate up to 200 ° C. can be controlled within 1 hour to control the desired particle size.
　反応終了後は、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 lower. 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.
　二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 dioxide-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 the 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).
〈破砕工程〉
　水熱反応により作製された二酸化バナジウム含有粒子を破砕する工程では、８０個数％以上の二酸化バナジウム含有粒子の粒径を５０ｎｍ以下とすることを特徴とする。
　二酸化バナジウム含有粒子を破砕する方法としては特に制限はないが、例えば、高速撹拌機、高圧ホモジナイザー、ビーズミル、振とう機等の装置を使用して行うことができる。中でも、粒子の微小化の観点で高圧ホモジナイザーやビーズミルを用いて破砕することが好ましい。 <Crushing process>
In the step of crushing the vanadium dioxide-containing particles produced by the hydrothermal reaction, the particle size of the vanadium dioxide-containing particles of 80% by number or more is 50 nm or less.
The method for crushing the vanadium dioxide-containing particles is not particularly limited, and can be performed using a device such as a high-speed stirrer, a high-pressure homogenizer, a bead mill, and a shaker. Among them, it is preferable to crush using a high-pressure homogenizer or a bead mill from the viewpoint of particle miniaturization.
　高圧ホモジナイザーとは、加速された高流速によるせん断力、急激な圧力降下（キャビテーション）及び高流速の粒子同士が微細オリフィス内で対面衝突することによる衝撃力によって磨砕を行う装置であり、市販されている装置としては、ナノマイザー（ナノマイザー株式会社製）、マイクロフルイダイザー（Ｍｉｃｒｏｆｌｕｉｄｉｃｓ社製）等を用いることができる。高圧ホモジナイザーによる破砕の程度は、高圧ホモジナイザーへ圧送する圧力と高圧ホモジナイザーに通過させる回数（パス回数）に依存する。 A high-pressure homogenizer is a commercially available device that grinds by shearing force due to accelerated high flow velocity, rapid pressure drop (cavitation), and impact force caused by high-velocity particles colliding face-to-face within a fine orifice. As the device, a nanomizer (manufactured by Nanomizer Co., Ltd.), a microfluidizer (manufactured by Microfluidics) or the like can be used. The degree of crushing by the high-pressure homogenizer depends on the pressure fed to the high-pressure homogenizer and the number of passes through the high-pressure homogenizer (number of passes).
　ビーズミルは、容器内にメディアとしてビーズを充填し、撹拌されているビーズ中に粒子と媒体からなるスラリーを流し込み、媒体中でビーズとともに撹拌することにより凝集粒子を砕いて粉砕、分散する工程を有する装置である。また、スラリーとビーズの分離に遠心分離を用いる装置もある。このようなビーズミルとしては、スターミルＺＲＳ（アシザワファインテック（株）製）、ウルトラアペックスミル（寿工業（株）製）、ＭＳＣ－ＭＩＬＬ（三井鉱山株式会社）などがある。 The bead mill has a step of filling a container with beads as a medium, pouring a slurry of particles and medium into the stirred beads, and crushing and pulverizing and dispersing the aggregated particles by stirring together with the beads in the medium. Device. There is also an apparatus that uses centrifugal separation to separate the slurry and beads. Examples of such a bead mill include Star Mill ZRS (manufactured by Ashizawa Finetech Co., Ltd.), Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.), and MSC-MILL (Mitsui Mining Co., Ltd.).
　ビーズミルで用いるビーズは特に限定されず、金属製、セラミック製等が挙げられるが、例えば、ジルコニアビーズ、アルミナビーズ等を用いることができる。
　ビーズの大きさは、目的に合わせて選定するが、例えば、適用するビーズの粒径としては０．０３～０．３ｍｍ程度のものが好ましい。
　ビーズミルを用いた破砕は、ビーズを容器内に１０～８０体積％の範囲内となるようにして用いるのが好ましい。
　また、ビーズミルでの処理時間は１０分間から２４時間程度が好ましく、これ以上の処理を行うとビーズからのコンタミが混入する可能性がある。 The beads used in the bead mill are not particularly limited, and examples thereof include metals and ceramics. For example, zirconia beads and alumina beads can be used.
The size of the beads is selected according to the purpose. For example, the particle size of the beads to be applied is preferably about 0.03 to 0.3 mm.
The crushing using a bead mill is preferably used such that the beads are in the range of 10 to 80% by volume in the container.
Further, the treatment time in the bead mill is preferably about 10 minutes to 24 hours, and if the treatment is further performed, contamination from the beads may be mixed.
　また、破砕時には必要に応じて、分散剤を添加することができる。市販のアニオン系界面活性剤、カチオン系界面活性剤、非イオン系界面活性剤、金属アルコキシドなどを好ましく用いることができる。分散剤の添加量は、粒子質量の４０質量％以下であることが好ましい。 Also, a dispersing agent can be added as needed during crushing. Commercially available anionic surfactants, cationic surfactants, nonionic surfactants, metal alkoxides and the like can be preferably used. The addition amount of the dispersant is preferably 40% by mass or less of the particle mass.
《二酸化バナジウム含有粒子》
　本発明に係る二酸化バナジウム含有粒子は、少なくとも二酸化バナジウムを含んで構成され、これにより、サーモクロミック性を発現することができる。
　二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（二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）の差（＝２５℃／５０％ＲＨにおける光透過率－８５℃／５０％ＲＨにおける光透過率）が３０％以上であることが好ましい。
　二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 dioxide-containing particles>
The vanadium dioxide-containing particles according to the present invention are configured to include at least vanadium dioxide, and thereby can exhibit thermochromic properties.
The thermochromic property of the vanadium dioxide-containing particles is not particularly limited as long as optical properties such as light transmittance and light reflectance change reversibly with temperature. For example, the difference in light transmittance (light transmittance of a film added with vanadium dioxide-containing particles) at 25 ° C./50% RH and 85 ° C./50% RH (= light transmittance at 25 ° C./50% RH−85 ° C. / Light transmittance at 50% RH) is preferably 30% or more.
The light transmittance of the film to which the vanadium dioxide-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).
　二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。 The light transmittance of the film to which the vanadium dioxide-containing particles are added is preferably as high as possible, but is preferably 70% or more.
　また、本発明に係る二酸化バナジウム含有粒子は、８０個数％以上の粒径が５０ｎｍ以下であることを特徴とする。このため、本発明に係る二酸化バナジウム含有粒子をウィンドウフィルムに混合して使用した場合であってもヘイズ値が小さく、また、欠損部位を最小限に止めているため、サーモクロミック性とその保存安定性を維持することができる。 Further, the vanadium dioxide-containing particles according to the present invention are characterized in that a particle size of 80% by number or more is 50 nm or less. For this reason, even when the vanadium dioxide-containing particles according to the present invention are used mixed with a window film, the haze value is small, and since the defect site is minimized, the thermochromic property and its storage stability Sex can be maintained.
《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 compound>
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、ギ酸、ヒドラジン、又はそれらの水和物であることが好ましい。 《Reducing agent》
Although it does not specifically limit as a reducing agent which concerns on this invention, It is preferable that they are oxalic acid, formic acid, hydrazine, or those hydrates.
　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、本実施例において、作製された粒子の粒径分布は、レーザー回折式粒度分布計を用いて測定した。具体的には、粒子を１質量％の濃度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。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
In this example, the particle size distribution of the produced particles was measured using a laser diffraction particle size distribution meter. Specifically, the particles were mixed with water so as to have a concentration of 1% by mass, dispersed with ultrasonic waves for 15 minutes to prepare a sample, and measured using a laser diffraction particle size distribution analyzer manufactured by Shimadzu Corporation. .
《サンプルの作製》
〈サンプル１０１の作製〉
　特許第５６２５１７２号公報の実施例１を参考にして、二酸化バナジウム粒子を作製した。
　この二酸化バナジウム粒子には、粒径が１００ｎｍ以下である粒子が３２個数％含まれていた。 <Production of sample>
<Preparation of Sample 101>
Vanadium dioxide particles were prepared with reference to Example 1 of Japanese Patent No. 5625172.
The vanadium dioxide particles contained 32% by number of particles having a particle size of 100 nm or less.
　作製した粒子にビーズミルを行い、粒子の破砕を行った。
　まず、粒子と水とを混合し、１０質量％の分散液５００ｍＬとした。この分散液に、粒径０．１ｍｍのジルコニアビーズを２００ｇ混合し、ウルトラアペックスミル（寿工業（株）製）を用いて、２０分間、破砕を行い、サンプル１０１を作製した。
　サンプル１０１は、８１個数％の二酸化バナジウム含有粒子の粒径が５０ｎｍ以下であった。 The produced particles were subjected to bead milling to crush the particles.
First, particles and water were mixed to make 500 mL of a 10% by mass dispersion. To this dispersion, 200 g of zirconia beads having a particle diameter of 0.1 mm was mixed, and crushed for 20 minutes using an Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) to prepare Sample 101.
In sample 101, the particle diameter of 81% by number of vanadium dioxide-containing particles was 50 nm or less.
〈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）０．５５ｇ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。
　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、２６０℃・４８時間の水熱反応を行った。
　この際、２５℃から２００℃までの昇温時間を３時間とした。
　この二酸化バナジウム含有粒子には、粒径が１００ｎｍ以下である粒子が３１個数％含まれていた。 <Preparation of Sample 102>
0.55 g of divanadium pentoxide (V) (V 2 O 5 , special grade, Wako Pure Chemical Industries) was added 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. In addition, after stirring at 30 ° C. for 4 hours, 2.4 mL of a 1.25 mol / L aqueous solution of hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.) was slowly added dropwise.
The prepared liquid mixture is put in a high-pressure reaction decomposition container stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample container HUTc-50: manufactured by Sanai Kagaku Co., Ltd.), and subjected to a hydrothermal reaction at 260 ° C. for 48 hours. went.
At this time, the temperature raising time from 25 ° C. to 200 ° C. was 3 hours.
The vanadium dioxide-containing particles contained 31% by number of particles having a particle size of 100 nm or less.
　反応後、得られた生成物について限外濾過を用いて洗浄を行い、二酸化バナジウム含有粒子の水分散液を調製した。 After the reaction, the obtained product was washed using ultrafiltration to prepare an aqueous dispersion of vanadium dioxide-containing particles.
　調製した分散液にビーズミルを行い、粒子の破砕を行った。
　まず、分散液を濃縮することで、１０質量％の分散液５００ｍＬとした。この分散液に、粒径０．１ｍｍのジルコニアビーズを２００ｇ混合し、ウルトラアペックスミル（寿工業（株）製）を用いて、１５分間、破砕を行い、サンプル１０２を作製した。
　サンプル１０２は、７３個数％の二酸化バナジウム含有粒子の粒径が５０ｎｍ以下であった。 The prepared dispersion was subjected to bead milling to crush the particles.
First, the dispersion was concentrated to 500 mL of a 10% by mass dispersion. 200 g of zirconia beads having a particle size of 0.1 mm was mixed with this dispersion, and crushing was performed for 15 minutes using an Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) to produce Sample 102.
In sample 102, the particle diameter of 73% by number of vanadium dioxide-containing particles was 50 nm or less.
〈サンプル１０３の作製〉
　サンプル１０２の作製において、ビーズミルによる破砕時間を２０分間とした以外は同様にして、サンプル１０３を作製した。
　破砕後のサンプル１０３は、８２個数％の二酸化バナジウム含有粒子の粒径が５０ｎｍ以下であった。 <Preparation of Sample 103>
Sample 103 was prepared in the same manner as in the preparation of sample 102, except that the crushing time by the bead mill was 20 minutes.
In the sample 103 after crushing, the particle size of 82% by number of vanadium dioxide-containing particles was 50 nm or less.
〈サンプル１０４の作製〉
　サンプル１０３の作製において、２５℃から２００℃までの昇温時間を１時間とした以外は同様にして、サンプル１０４を作製した。
　水熱反応直後の二酸化バナジウム含有粒子には、粒径が１００ｎｍ以下である粒子が７２個数％含まれていた。
　また、破砕後のサンプル１０４は、８１個数％の二酸化バナジウム含有粒子の粒径が５０ｎｍ以下であった。 <Preparation of Sample 104>
Sample 104 was prepared in the same manner as in the preparation of Sample 103 except that the temperature raising time from 25 ° C. to 200 ° C. was set to 1 hour.
The vanadium dioxide-containing particles immediately after the hydrothermal reaction contained 72% by number of particles having a particle size of 100 nm or less.
Further, in the sample 104 after crushing, the particle size of 81% by number of vanadium dioxide-containing particles was 50 nm or less.
〈サンプル１０５の作製〉
　サンプル１０４の作製において、ビーズミルによる破砕時間を４５分間とした以外は同様にして、サンプル１０５を作製した。
　破砕後のサンプル１０５は、９２個数％の二酸化バナジウム含有粒子の粒径が５０ｎｍ以下であった。 <Preparation of Sample 105>
Sample 105 was prepared in the same manner as in the preparation of sample 104 except that the crushing time by the bead mill was 45 minutes.
In the sample 105 after crushing, the particle size of 92% by number of vanadium dioxide-containing particles was 50 nm or less.
〈サンプル１０６の作製〉
　サンプル１０５の作製において、２５℃から２００℃までの昇温時間を４５分間とした以外は同様にして、サンプル１０６を作製した。
　水熱反応直後の二酸化バナジウム含有粒子には、粒径が１００ｎｍ以下である粒子が８１個数％含まれていた。
　また、破砕後のサンプル１０６は、９１個数％の二酸化バナジウム含有粒子の粒径が５０ｎｍ以下であった。 <Preparation of Sample 106>
Sample 106 was produced in the same manner as in the production of sample 105 except that the temperature raising time from 25 ° C. to 200 ° C. was changed to 45 minutes.
The vanadium dioxide-containing particles immediately after the hydrothermal reaction contained 81% by number of particles having a particle size of 100 nm or less.
In the sample 106 after crushing, the particle size of 91% by number of vanadium dioxide-containing particles was 50 nm or less.
〈サンプル１０７の作製〉
　サンプル１０５の作製において、以下のようにして水熱反応を行った以外は同様にして、サンプル１０７を作製した。 <Preparation of Sample 107>
Sample 107 was produced in the same manner as in the production of sample 105 except that the hydrothermal reaction was performed as follows.
　３５質量％の過酸化水素水（和光純薬社製）２ｍＬと純水２０ｍＬ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、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３．０ｍＬゆっくり滴下した。
　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、２６０℃・４８時間の水熱反応を行った。
　この際、２５℃から２００℃までの昇温時間を１時間とした。 0.55 g of divanadium pentoxide (V) (V 2 O 5 , special grade, Wako Pure Chemical Industries) was added to an aqueous solution obtained by mixing 2 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 mL of pure water. In addition, after stirring at 30 ° C. for 4 hours, 3.0 mL of a 1.25 mol / L aqueous solution of oxalic acid dihydrate (H 2 C 2 O 4 .2H 2 O, manufactured by Wako Pure Chemical Industries, Ltd., special grade) was slowly added dropwise. .
The prepared liquid mixture is put in a high-pressure reaction decomposition container stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample container HUTc-50: manufactured by Sanai Kagaku Co., Ltd.), and subjected to a hydrothermal reaction at 260 ° C. for 48 hours. went.
At this time, the temperature raising time from 25 ° C. to 200 ° C. was set to 1 hour.
　水熱反応直後の二酸化バナジウム含有粒子には、粒径が１００ｎｍ以下である粒子が７１個数％含まれていた。
　また、破砕後のサンプル１０７は、９１個数％の二酸化バナジウム含有粒子の粒径が５０ｎｍ以下であった。 The vanadium dioxide-containing particles immediately after the hydrothermal reaction contained 71% by number of particles having a particle size of 100 nm or less.
Further, in the sample 107 after crushing, the particle size of 91% by number of vanadium dioxide-containing particles was 50 nm or less.
〈サンプル１０８の作製〉
　サンプル１０５の作製において、以下のようにして水熱反応を行った以外は同様にして、サンプル１０８を作製した。 <Preparation of Sample 108>
Sample 108 was produced in the same manner as in the production of sample 105 except that the hydrothermal reaction was performed as follows.
　３５質量％の過酸化水素水（和光純薬社製）２ｍＬと純水２０ｍＬ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、ギ酸（ＨＣＯＯＨ、和光純薬社製、特級）の１．２５ｍｏｌ／Ｌ水溶液を３．０ｍＬゆっくり滴下した。
　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、２６０℃・４８時間の水熱反応を行った。
　この際、２５℃から２００℃までの昇温時間を１時間とした。 0.55 g of divanadium pentoxide (V) (V 2 O 5 , special grade, Wako Pure Chemical Industries) was added to an aqueous solution obtained by mixing 2 mL of 35% by mass of hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 mL of pure water. In addition, after stirring at 30 ° C. for 4 hours, 3.0 mL of a 1.25 mol / L aqueous solution of formic acid (HCOOH, manufactured by Wako Pure Chemical Industries, Ltd., special grade) was slowly added dropwise.
The prepared liquid mixture is put in a high-pressure reaction decomposition container stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample container HUTc-50: manufactured by Sanai Kagaku Co., Ltd.), and subjected to a hydrothermal reaction at 260 ° C. for 48 hours. went.
At this time, the temperature raising time from 25 ° C. to 200 ° C. was set to 1 hour.
　水熱反応直後の二酸化バナジウム含有粒子には、粒径が１００ｎｍ以下である粒子が７２個数％含まれていた。
　また、破砕後のサンプル１０８は、９２個数％の二酸化バナジウム含有粒子の粒径が５０ｎｍ以下であった。 The vanadium dioxide-containing particles immediately after the hydrothermal reaction contained 72% by number of particles having a particle size of 100 nm or less.
In the sample 108 after crushing, the particle size of 92% by number of vanadium dioxide-containing particles was 50 nm or less.
《評価》
〈ヘイズ値の測定〉
　作製した各サンプルについて、粒子濃度が５質量％となるように純水を加え、分散液を調製した。分散液２０ｇを、９０ｇの１０質量％ポリビニルアルコール水溶液と混合し、塗布液を調製した。ポリエチレンテレフタレートフィルム（厚さ５０μｍ）上に、上記塗布液を乾燥後膜厚が５μｍとなるようにワイヤーバーで塗布し、６０℃で２４時間乾燥して測定用フィルムとした。なお、上記塗布液を塗布・乾燥して形成される層中の二酸化バナジウム含有粒子の含有量は、当該層の固形分に対して１０質量％となるように調整した。
　この測定用フィルムを用いて、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。ヘイズ値は、小さいほど透明フィルムとして良好であることを示す。
　評価結果を表１に示す。 <Evaluation>
<Measurement of haze value>
About each produced sample, the pure water was added so that particle concentration might be 5 mass%, and the dispersion liquid was prepared. 20 g of the dispersion was mixed with 90 g of a 10% by mass aqueous polyvinyl alcohol solution to prepare a coating solution. On a polyethylene terephthalate film (thickness 50 μm), the coating solution was applied with a wire bar so that the film thickness was 5 μm after drying, and dried at 60 ° C. for 24 hours to obtain a measurement film. In addition, content of the vanadium dioxide containing particle | grains in the layer formed by apply | coating and drying the said coating liquid was adjusted so that it might become 10 mass% with respect to solid content of the said layer.
Using this film for measurement, a haze value (%) was measured using a haze meter NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd., and evaluated according to the following evaluation criteria. A smaller haze value indicates a better transparent film.
The evaluation results are shown in Table 1.
　◎：４％未満
　○：４％以上７％未満
　×：７％以上 ◎: Less than 4% ○: 4% or more and less than 7% ×: 7% or more
〈サーモクロミック性〉
　上記で作製した各測定用フィルムを用いて、２５℃／５０％ＲＨ及び８５℃／５０％ＲＨの各条件における波長２０００ｎｍでのそれぞれの光透過率（％）を測定した後、光透過率差ΔＴ（％）（＝２５℃／５０％ＲＨにおける光透過率－８５℃／５０％ＲＨにおける光透過率）を算出し、下記評価基準に従って評価した。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。
　評価結果を表１に示す。 <Thermochromic properties>
After measuring each light transmittance (%) at a wavelength of 2000 nm in each condition of 25 ° C./50% RH and 85 ° C./50% RH using each measurement film produced above, the difference in light transmittance ΔT (%) (= light transmittance at 25 ° C./50% RH−light transmittance at 85 ° C./50% RH) was calculated and evaluated according to the following evaluation criteria. The light transmittance was measured 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.
　◎：３５．０％以上
　○：３０．０％以上３５．０％未満
　△：２０．０％以上３０．０％未満
　×：２０．０％未満 ◎: 35.0% or more ○: 30.0% or more and less than 35.0% △: 20.0% or more and less than 30.0% ×: Less than 20.0%
〈サーモクロミック性の保存安定性〉
　上記で作製した各測定用フィルムを６０℃／９０％ＲＨ下に１０００時間保存した後の光透過率差（ΔＴ（％））を上記サーモクロミック性の評価と同様にして算出し、保存前後でのサーモクロミック性の保持率（光透過率差（％）の減少幅）（％）を下記評価基準に従って評価した。
　なお、サーモクロミック性の保持率（％）は、下記式に従って算出した。
　評価結果を表１に示す。 <Thermochromic storage stability>
The light transmittance difference (ΔT (%)) after storing each measurement film prepared above at 60 ° C./90% RH for 1000 hours was calculated in the same manner as the thermochromic evaluation, before and after storage. The thermochromic retention rate (reduction of light transmittance difference (%)) (%) was evaluated according to the following evaluation criteria.
The thermochromic retention rate (%) was calculated according to the following formula.
The evaluation results are shown in Table 1.
　保持率（％）＝（保存後のΔＴ（％））／（保存前のΔＴ（％））×１００ Retention rate (%) = (ΔT (%) after storage) / (ΔT (%) before storage) × 100
　◎：９０．０％以上
　○：７０．０％以上９０．０％未満
　△：５０．０％以上７０．０％未満
　×：５０．０％未満 ◎: 90.0% or more ○: 70.0% or more and less than 90.0% △: 50.0% or more and less than 70.0% ×: Less than 50.0%
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１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の製造方法により製造されたサンプル１０３～１０８は、比較例のサンプル１０１及び１０２と比較して、サーモクロミック性及びその保存安定性に優れていることが示されている。サンプル１０１は、破砕前の二酸化バナジウム含有粒子を水熱方法ではなく、焼成により作製しているため、破砕による粒子の劣化（欠損部位）が大きく、その結果、サーモクロミック性及びその保存安定性が低下している。また、サンプル１０２は、破砕時間を短縮しているため、破砕による劣化が少なく、サンプル１０３と同程度の保存安定性が得られているが、粒径が大きいため、ヘイズ値が大きく、サーモクロミック性も悪くなっている。
　以上から、水熱反応により、二酸化バナジウム含有粒子を形成する工程と、二酸化バナジウム含有粒子を破砕する工程と、を有し、二酸化バナジウム含有粒子を破砕する工程では、８０個数％以上の二酸化バナジウム含有粒子の粒径を５０ｎｍ以下とする二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保存安定性に優れた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。 As is apparent from Table 1, the samples 103 to 108 produced by the method for producing vanadium dioxide-containing particles of the present invention are superior in thermochromic properties and their storage stability compared to the samples 101 and 102 of the comparative examples. It is shown that. In sample 101, vanadium dioxide-containing particles before crushing are produced by firing instead of the hydrothermal method. Therefore, particle deterioration (defect site) due to crushing is large, and as a result, thermochromic properties and storage stability thereof are improved. It is falling. In addition, since the sample 102 shortens the crushing time, the deterioration due to crushing is small and the same storage stability as that of the sample 103 is obtained. However, since the particle size is large, the haze value is large, and the thermochromic The nature is also getting worse.
From the above, in the step of forming vanadium dioxide-containing particles by hydrothermal reaction and the step of crushing vanadium dioxide-containing particles, the step of crushing vanadium dioxide-containing particles contains 80% or more vanadium dioxide. It can be seen that the method for producing vanadium dioxide-containing particles having a particle size of 50 nm or less is useful for providing vanadium dioxide-containing particles having excellent thermochromic properties and storage stability.
　本発明は、サーモクロミック性及び保存安定性に優れた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 can be particularly suitably used for providing a method for producing vanadium dioxide-containing particles having excellent thermochromic properties and storage stability.

Claims (5)

  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の製造方法であって、
    　水熱反応により、二酸化バナジウム含有粒子を形成する工程と、
    　前記二酸化バナジウム含有粒子を破砕する工程と、
    を有し、
    　前記二酸化バナジウム含有粒子を破砕する工程では、８０個数％以上の前記二酸化バナジウム含有粒子の粒径を５０ｎｍ以下とす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,
    Forming vanadium dioxide-containing particles by a hydrothermal reaction;
    Crushing the vanadium dioxide-containing particles;
    Have
    In the step of crushing the vanadium dioxide-containing particles, the particle size of the vanadium dioxide-containing particles of 80% by number or more is set to 50 nm or less.
  2. 　前記二酸化バナジウム含有粒子を形成する工程では、水熱反応により、粒径が１００ｎｍ以下である二酸化バナジウム含有粒子を７０個数％以上形成することを特徴とする請求項１に記載の二酸化バナジウム含有粒子の製造方法。 2. The vanadium dioxide-containing particles according to claim 1, wherein in the step of forming the vanadium dioxide-containing particles, 70% by number or more of vanadium dioxide-containing particles having a particle size of 100 nm or less is formed by a hydrothermal reaction. Production method.
  3. 　前記二酸化バナジウム含有粒子を形成する工程では、少なくとも、バナジウム化合物と還元剤と水とを混合して水熱反応させることを特徴とする請求項１又は請求項２に記載の二酸化バナジウム含有粒子の製造方法。 3. The production of vanadium dioxide-containing particles according to claim 1, wherein in the step of forming the vanadium dioxide-containing particles, at least a vanadium compound, a reducing agent, and water are mixed and subjected to a hydrothermal reaction. Method.
  4. 　前記還元剤が、シュウ酸、ギ酸、ヒドラジン、又はそれらの水和物であることを特徴とする請求項３に記載の二酸化バナジウム含有粒子の製造方法。 The method for producing particles containing vanadium dioxide according to claim 3, wherein the reducing agent is oxalic acid, formic acid, hydrazine, or a hydrate thereof.
  5. 　前記二酸化バナジウム含有粒子を形成する工程では、２３０℃以上で水熱反応を行い、かつ、反応系が２５℃から２００℃に到達するまでの時間を１時間以内とすることを特徴とする請求項１から請求項４までのいずれか一項に記載の二酸化バナジウム含有粒子の製造方法。 The step of forming the vanadium dioxide-containing particles performs a hydrothermal reaction at 230 ° C or higher, and a time until the reaction system reaches from 25 ° C to 200 ° C is within one hour. The manufacturing method of the vanadium dioxide containing particle | grains as described in any one of Claim 1- Claim 4.
PCT/JP2016/084062 2015-11-20 2016-11-17 Method for producing vanadium dioxide-containing particles WO2017086376A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201680066573.1A CN108349745B (en) 2015-11-20 2016-11-17 Method for producing vanadium dioxide-containing particles
JP2017551918A JPWO2017086376A1 (en) 2015-11-20 2016-11-17 Method for producing vanadium dioxide-containing particles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015227185 2015-11-20
JP2015-227185 2015-11-20

Publications (1)

Publication Number Publication Date
WO2017086376A1 true WO2017086376A1 (en) 2017-05-26

Family

ID=58718894

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/084062 WO2017086376A1 (en) 2015-11-20 2016-11-17 Method for producing vanadium dioxide-containing particles

Country Status (3)

Country Link
JP (1) JPWO2017086376A1 (en)
CN (1) CN108349745B (en)
WO (1) WO2017086376A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010031235A (en) * 2008-06-30 2010-02-12 National Institute Of Advanced Industrial & Technology Thermochromic microparticle, dispersion thereof, and manufacturing method thereof, as well as dimming coating, dimming film and dimming ink
JP2011136873A (en) * 2009-12-28 2011-07-14 Tsurumi Soda Co Ltd Vanadium dioxide fine particles, manufacturing method and thermo-chromic film
JP2014080350A (en) * 2012-09-28 2014-05-08 Sekisui Chem Co Ltd Vanadium oxide particle
JP2014094881A (en) * 2012-10-11 2014-05-22 Sekisui Chem Co Ltd Method for manufacturing vanadium dioxide particles
JP2015063455A (en) * 2013-08-30 2015-04-09 積水化学工業株式会社 Method for producing vanadium dioxide fine particle having thermochromic properties

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5989514A (en) * 1997-07-21 1999-11-23 Nanogram Corporation Processing of vanadium oxide particles with heat
WO2005060610A2 (en) * 2003-12-11 2005-07-07 The Trustees Of Columbia University In The City Ofnew York Nano-sized particles, processes of making, compositions and uses thereof
JP5548479B2 (en) * 2010-02-26 2014-07-16 独立行政法人産業技術総合研究所 Method for producing single crystal fine particles
JP5781837B2 (en) * 2011-06-03 2015-09-24 積水化学工業株式会社 Thermochromic film, interlayer film for laminated glass, laminated glass and film for pasting
CN103157480B (en) * 2013-02-04 2015-02-18 合肥工业大学 Vanadium oxide/iron oxide denitration catalyst, preparation method and application thereof
CN104261693B (en) * 2014-08-28 2016-08-17 中国科学院上海硅酸盐研究所 A kind of hypovanadic oxide-based thermochromism composite granule and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010031235A (en) * 2008-06-30 2010-02-12 National Institute Of Advanced Industrial & Technology Thermochromic microparticle, dispersion thereof, and manufacturing method thereof, as well as dimming coating, dimming film and dimming ink
JP2011136873A (en) * 2009-12-28 2011-07-14 Tsurumi Soda Co Ltd Vanadium dioxide fine particles, manufacturing method and thermo-chromic film
JP2014080350A (en) * 2012-09-28 2014-05-08 Sekisui Chem Co Ltd Vanadium oxide particle
JP2014094881A (en) * 2012-10-11 2014-05-22 Sekisui Chem Co Ltd Method for manufacturing vanadium dioxide particles
JP2015063455A (en) * 2013-08-30 2015-04-09 積水化学工業株式会社 Method for producing vanadium dioxide fine particle having thermochromic properties

Also Published As

Publication number Publication date
CN108349745A (en) 2018-07-31
JPWO2017086376A1 (en) 2018-09-06
CN108349745B (en) 2021-02-02

Similar Documents

Publication Publication Date Title
JP5077941B2 (en) Core-shell type cerium oxide fine particles or dispersion containing the same and method for producing them
US9909033B2 (en) Liquid suspensions and powders of cerium oxide particles and preparation and polishing applications thereof
JP4701409B2 (en) Core-shell cerium oxide polymer hybrid nanoparticles and method for producing dispersion thereof
JP2010513718A (en) Method for producing monodisperse and stable nanometallic silver and product obtained by said method
US5653793A (en) TiO2 slurry process
KR102068386B1 (en) Method of synthesizing nano-sized particles
JP6959290B2 (en) Monoclinic zirconia nanoparticles and their manufacturing methods
JP6927687B2 (en) Nanodiamond dispersion liquid manufacturing method and nanodiamond dispersion liquid
JP7196861B2 (en) CORE-SHELL PARTICLES, METHOD FOR PRODUCING SAME, AND COMPOSITION
JP2011063496A (en) Anatase-type titanium dioxide hyperfine particle, dispersion containing the same and method for producing the titanium dioxide
JP5392696B2 (en) Core-shell type cobalt oxide fine particles or dispersion containing the same, production method and use thereof
Xie et al. A novel method for the preparation of Bi4Ti3O12 nanoparticles in w/o microemulsion
JP2017001916A (en) Method for producing nanodiamond powder and the nanodiamond powder
JP2018002952A (en) Method for producing vanadium dioxide-containing particles
WO2017086376A1 (en) Method for producing vanadium dioxide-containing particles
JP2017202940A (en) Nano diamond production method
WO2016152865A1 (en) Method for producing vanadium dioxide-containing particles
He et al. Preparation and characterization of monodisperse zirconia spherical nanometer powder via lamellar liquid crystal template method
JP5474310B2 (en) Granular barium carbonate composition powder
JP5895557B2 (en) Particulate composition, method for producing particulate composition, and particulate composition dispersion
JP2017110144A (en) Method for producing vanadium dioxide-containing grain
Sharova et al. Liquid metal-mediated fabrication of metalloid nanoarchitectures
JP2016166294A (en) Method of producing vanadium oxide-containing particle and vanadium oxide-containing particle
JP2017226771A (en) Production method of fluid dispersion of vanadium dioxide-containing particles
JP6257243B2 (en) Rare earth titanate powder, method for producing the same, and dispersion containing the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16866377

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017551918

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16866377

Country of ref document: EP

Kind code of ref document: A1