WO2017208892A1 - Procédé de production de particules contenant du dioxyde de vanadium - Google Patents

Procédé de production de particules contenant du dioxyde de vanadium Download PDF

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Publication number
WO2017208892A1
WO2017208892A1 PCT/JP2017/019096 JP2017019096W WO2017208892A1 WO 2017208892 A1 WO2017208892 A1 WO 2017208892A1 JP 2017019096 W JP2017019096 W JP 2017019096W WO 2017208892 A1 WO2017208892 A1 WO 2017208892A1
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Prior art keywords
vanadium dioxide
vanadium
containing particles
raw material
material liquid
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PCT/JP2017/019096
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English (en)
Japanese (ja)
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智広 工藤
千葉　隆人
保彦 高向
林　健司
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コニカミノルタ株式会社
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Priority to JP2018520813A priority Critical patent/JP7001052B2/ja
Priority to CN201780033357.1A priority patent/CN109195917B/zh
Publication of WO2017208892A1 publication Critical patent/WO2017208892A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • 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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method for producing vanadium dioxide-containing particles that produces vanadium dioxide-containing particles having no aggregation, a narrow particle size distribution, and excellent thermochromic properties by a hydrothermal synthesis method using a flow reactor.
  • thermochromic materials are being actively studied.
  • thermochromic material is a material that can control, for example, optical characteristics typified by light transmittance by temperature.
  • the infrared energy is reflected in the summer to block the heat entering the room, and the infrared energy is transmitted into the room in the winter to use the thermal energy. Is possible.
  • thermochromic materials a material containing vanadium dioxide (VO 2 ) can be given as one of the thermochromic materials that have attracted the most attention.
  • This vanadium dioxide is known to exhibit “thermochromic properties”, which is a property in which optical properties reversibly change with temperature when a phase transition occurs near room temperature. Therefore, by utilizing this property, a material exhibiting environmental temperature-dependent thermochromic characteristics can be obtained.
  • vanadium dioxide has several crystal phases such as an A phase, a B phase, a C phase, and a rutile type crystal phase (hereinafter also referred to as “R phase”).
  • the crystal structure exhibiting chromic properties at a relatively low temperature of 100 ° C. or lower is limited to the R phase (rutile crystal phase).
  • This R phase has a monoclinic structure below the phase transition temperature (about 68 ° C.), and exhibits high visible light and infrared transmittance.
  • the R phase has a tetragonal structure at a temperature of 68 ° C. or more, which is a phase transition temperature, and exhibits a property of low infrared transmittance as compared with a monoclinic structure. That is, it has a unique property that the infrared transmittance changes greatly at the phase transition temperature.
  • the vanadium dioxide-containing particles having such characteristics are applied to an optical film that is used by being attached to a window glass or the like, transparency as particles (low haze) is required. It is desirable that the vanadium-containing particles are not aggregated (secondary particle size is small) and the particle size is nano-order (100 nm or less).
  • Patent Document 1 discloses that the size and shape of the powder are obtained by setting the composition of the doping vanadium dioxide powder (V 1-x M x O 2 ) so that the doping element satisfies 0 ⁇ x ⁇ 0.5. Is disclosed to be controllable. As a result, it is disclosed that the crystal grain size of the doped vanadium dioxide powder produced can be reduced and made uniform. And as a manufacturing method of doping vanadium dioxide powder, after the reaction precursor processed so that a hydrothermal reaction can be performed more easily is transferred to a hydrothermal reaction autoclave, and a hydrothermal reaction is performed, a hydrothermal reaction product is used. A method for dry separation is disclosed.
  • Patent Document 1 is a batch-type production apparatus using a hydrothermal autoclave and is a production method requiring a long hydrothermal reaction time of 6 to 12 hours. Since the average particle size is large and the distribution is wide, when the vanadium dioxide-containing particles are applied to an optical film, the haze is high, which is unsuitable as a film for use in vehicles or for building materials.
  • Patent Document 2 discloses a method for producing vanadium dioxide by a hydrothermal reaction using a solution containing vanadium, a hydrazine derivative and water.
  • Patent Document 2 is a method in which an autoclave is used as a hydrothermal reaction treatment apparatus and the production takes about 48 hours at 270 ° C. The production takes time and the vanadium dioxide obtained is obtained.
  • the average particle diameter is large and the distribution is wide, when the vanadium dioxide-containing particles are applied to an optical film, the haze is high, and it is not suitable as a film for use in vehicles or for building materials.
  • a method for producing functional metal fine particles a method using a flow reactor capable of producing fine particles in a short time is known.
  • a starting material slurry raw material liquid
  • a metal oxide sol a metal salt, a metal hydroxide sol, etc.
  • a method for producing conductive metal oxide fine particles is disclosed.
  • a heat treatment a starting material and supercritical water are mixed under a temperature of 200 ° C. or higher and a pressure of 10 MPa or more, and the temperature rise and heat treatment are performed within 2 minutes.
  • IZTO indium / zinc / tin oxide
  • Patent Document 4 a raw material aqueous solution containing Ba, Ca, Ti and Zr is continuously supplied together with water to a flow reactor, and reacted under hydrothermal conditions at a temperature of 250 ° C. or higher.
  • a method for producing nanoparticles of barium calcium zirconate is disclosed.
  • Patent Document 5 discloses a hydrothermal synthesis method using high-temperature and high-pressure water in a supercritical state as a production method using a flow reactor.
  • functional nanoparticle particles are prepared by supplying an alkaline aqueous solution to the reaction field and adjusting the pH during fine particle synthesis. This is a method to control the diameter, but it does not remove excess salts in the particle formation process, and the particles are formed in the same environment, so the crystallite diameter and particle diameter of the particles are set to the desired conditions.
  • the particle size distribution becomes wide, resulting in a decrease in thermochromic properties and a decrease in transparency (haze) when applied to an optical film.
  • Patent Document 3 and Patent Document 4 for the manufacture of particles containing vanadium dioxide (VO 2) having a thermochromic, applying a flow reactor, monodispersity is high, particles of vanadium dioxide ( There is no mention or disclosure regarding the method for obtaining VO 2 ) and specific heat treatment conditions, and the establishment of production conditions is urgently required.
  • the present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is that the average particle size is small, the formation of aggregates is suppressed, the particle size distribution is narrow, monodispersity and dispersion stability.
  • An object of the present invention is to provide a method for producing vanadium dioxide-containing particles which are excellent and have excellent thermochromic properties.
  • the present inventor uses a flow-type reaction apparatus having a hydrothermal reaction part, and a slurry raw material liquid containing at least a vanadium-containing compound and water, and A method for producing vanadium dioxide-containing particles, wherein a vanadium dioxide-containing particle is produced by a hydrothermal synthesis method using a reaction liquid obtained by mixing a compound that reacts with a vanadium-containing compound and supercritical or subcritical water,
  • the method for producing vanadium dioxide-containing particles is characterized in that the vanadium dioxide-containing particles are produced by at least one method selected from the following production conditions 1 to 4.
  • the present inventors have found a method for producing vanadium dioxide-containing particles having a narrow diameter distribution, excellent monodispersibility and dispersion stability, and excellent thermochromic properties.
  • a method for producing vanadium dioxide-containing particles using a liquid and producing vanadium dioxide-containing particles by a hydrothermal synthesis method A method for producing vanadium dioxide-containing particles, comprising producing vanadium dioxide-containing particles by at least one method selected from the following production conditions 1 to 4.
  • Manufacturing condition 1 Deaerated water that has been subjected to a deaeration process is used as the water constituting the reaction solution.
  • Manufacturing condition 2 The passage time of the hydrothermal reaction section in which the hydrothermal synthesis method is performed using the reaction solution is set within a range of 3 to 1000 seconds.
  • Production condition 3 Before the slurry raw material liquid is processed by the hydrothermal synthesis method, a desalting treatment is performed to remove salts from the slurry raw material liquid, and the average primary particle diameter of the vanadium dioxide-containing particles is 15 to 40 nm. The average crystallite diameter should be adjusted so as to fall within the range of 15 to 40 nm.
  • Manufacturing condition 4 Before the step of manufacturing the vanadium dioxide-containing particles, the step of dispersing the slurry raw material liquid and adjusting the particle size distribution width of the vanadium dioxide-containing particles to 80 nm or less.
  • the dissolved oxygen amount at 25 ° C. of the degassed water constituting the reaction solution is 2.0 mg / L or less, any one of items 1 to 3
  • the Reynolds number Re of the reaction solution passing through the piping of the hydrothermal reaction section is in the range of 1000 to 45000, characterized in that The manufacturing method of the vanadium dioxide containing particle
  • a compound that reacts with the vanadium-containing compound is added to the supercritical or subcritical water, and in the production condition 1, the water is deaerated water.
  • the vanadium-containing compound is a vanadium (IV) -containing compound, and the compound that reacts with the vanadium-containing compound is an alkali.
  • the vanadium-containing compound is a vanadium (V) -containing compound, and the compound that reacts with the vanadium-containing compound is a reducing agent.
  • the average primary particle size of the vanadium dioxide-containing particles is in the range of 1 to 40 nm.
  • the slurry raw material liquid is subjected to a dispersion treatment by high-pressure dispersion treatment, any one of items 1, 16, and 17
  • the hydrothermal reaction is usually performed at a saturated vapor pressure at the reaction temperature. ing. Under such conditions, a long hydrothermal reaction is required, and in the period of the hydrothermal reaction, some of the precipitated vanadium dioxide microcrystals grow greatly. As a result, the produced vanadium dioxide-containing particles contain a component having a large particle size and have a wide particle size distribution.
  • the vanadium dioxide-containing particles are visible light due to the presence of some non-uniform particle size components.
  • the transparency of the optical film containing the vanadium dioxide-containing particles is not sufficiently improved.
  • a predetermined element is used. It was essential to control the size and shape of the doped vanadium dioxide powder by doping, and lacked versatility.
  • the production condition 2 (embodiment 2) according to the present invention, using a flow reactor having a hydrothermal reaction part for hydrothermal synthesis, a raw material liquid containing a vanadium-containing compound and water, Using a reaction solution in which a compound that reacts with a vanadium-containing compound and water in a supercritical or subcritical state is mixed, the reaction solution is allowed to pass through the hydrothermal reaction section of the flow reactor within a range of 3 to 1000 seconds. A hydrothermal reaction is performed.
  • thermochromic properties can be obtained due to the large surface area of the particles due to the vanadium dioxide-containing particles having both a narrow particle size distribution and a small particle size. Due to the diameter and the uniformity of the particle diameter, the light scattering property in the visible light region can be kept low, so that high transparency of the optical film containing vanadium dioxide-containing particles can be obtained. Moreover, patent document 3 and patent document 4 do not disclose at all about the idea and specific conditions for producing vanadium dioxide-containing particles using a flow reactor by such a technical idea.
  • the vanadium dioxide-containing particles are produced by a hydrothermal synthesis method, for example, if the slurry raw material liquid composed of a vanadium-containing compound, an alkali agent, etc. is in a state containing a large amount of salts, the salts are converted into water. It has been difficult to obtain vanadium dioxide-containing particles having a desired particle profile, which affects the control of the particle size during thermal synthesis, particularly the formation of crystallites.
  • thermochromic property is lowered, and conversely, if the crystallite diameter is too large (greater than 40 nm), in conjunction with this, Since a primary particle diameter exceeds 40 nm, as an optical film (thermochromic film), a haze becomes high and will have a problem.
  • the present inventor performs a desalting treatment on a slurry raw material liquid composed of a vanadium-containing compound, an alkali agent, and the like, before performing the treatment by the hydrothermal synthesis method.
  • a desalting treatment on a slurry raw material liquid composed of a vanadium-containing compound, an alkali agent, and the like, before performing the treatment by the hydrothermal synthesis method.
  • the particle formation environment during hydrothermal synthesis is optimized, and the average particle size of the vanadium dioxide-containing particles is adjusted within the range of 15 to 40 nm, and the average crystallite size is adjusted within the range of 15 to 40 nm.
  • thermochromic properties and transparency when used as an optical film, and by setting the vanadium dioxide-containing particles to an optimum particle size range, hydrothermal synthesis, for example, a flow reactor , The blockage of the flow path due to particle aggregation or the like could be prevented, and continuous productivity could be improved.
  • the production mechanism and the action mechanism of the effect capable of solving the above-mentioned problems are presumed as follows according to the production condition 4 (embodiment 4).
  • the slurry raw material liquid dispersed in the supercritical or subcritical state using the step of dispersing the slurry raw material liquid and the flow reactor having the hydrothermal reaction section, And a step of producing a vanadium dioxide-containing particle by hydrothermally reacting the reaction mixture.
  • the particle size distribution of the vanadium dioxide-containing particles is widened, and as a result, the thermochromic property is lowered. Further, when the vanadium dioxide-containing particles are applied to an optical film, the particles are aggregated, so that sufficient transparency cannot be obtained. In addition, the specific surface area decreases due to aggregation, and sufficient thermochromic properties cannot be obtained.
  • the slurry raw material liquid is subjected to a dispersion treatment in advance before performing hydrothermal synthesis using a flow reactor, and the dispersed particle size of the vanadium-containing compound in the slurry raw material liquid. It is considered that by reducing the size, the particle size distribution width of the vanadium dioxide-containing particles after hydrothermal synthesis can be narrowed and the thermochromic property can be improved.
  • grains of this invention The figure which shows another example of the manufacturing flow in the manufacturing conditions 1 (embodiment 1) of the vanadium dioxide containing particle
  • Schematic shows an example of the flow-type reaction apparatus which comprised the hydrothermal reaction part applicable to manufacture of the vanadium dioxide containing particle
  • Process flow figure which shows an example of the manufacturing process of the manufacturing conditions 3 (embodiment 3) of the vanadium dioxide containing particle
  • Schematic which shows the processing flow of the ultrafiltration apparatus which is an example of the desalination apparatus used for the manufacturing conditions 3 of the vanadium dioxide containing particle
  • Schematic which shows an example of the manufacturing flow which comprised the hydrothermal reaction part applicable to the manufacturing conditions 3 of the vanadium dioxide containing particle
  • the schematic diagram which shows an example of the particle structure (crystallite diameter) of the vanadium dioxide containing particle
  • the graph which shows an example of the particle size distribution of the vanadium dioxide containing particle
  • the method for producing vanadium dioxide-containing particles of the present invention uses a flow reactor having a hydrothermal reaction section, a raw material liquid containing at least a vanadium-containing compound and water, a compound that reacts with the vanadium-containing compound, and a supercritical Alternatively, a method for producing vanadium dioxide-containing particles by a hydrothermal synthesis method using a reaction solution mixed with water in a subcritical state, wherein the production conditions 1 to 4 (embodiments 1 to 4) are used.
  • the vanadium dioxide-containing particles are produced by at least one method selected from: This feature is a technical feature common to or corresponding to each claim.
  • Embodiment 1 of the present invention from the viewpoint of manifesting the effects of the present invention, a method in which a compound that reacts with the vanadium-containing compound is added to a raw material liquid containing the vanadium-containing compound and degassed water (implementation).
  • Aspect 1A) or a method in which the compound that reacts with the vanadium-containing compound is added to the degassed water in the supercritical or subcritical state stabilizes the object effect of the present invention. It is preferable in that it can be expressed.
  • deaerated water having a desired dissolved oxygen amount can be obtained by preparing deaerated water to be applied by deaeration treatment using a deaeration membrane.
  • the amount of dissolved oxygen at 25 ° C. in the deaerated water constituting the reaction solution is 2.0 mg / L or less, more preferably 0.4 mg / L or less. It is preferable in that the vanadium dioxide-containing particles can be stably produced using a flow reactor.
  • the temperature of the reaction liquid in the hydrothermal reaction section of the flow reactor can be set within the range of 250 to 500 ° C., so that the hydrothermal reaction can be performed stably. This is preferable.
  • Embodiment 2 of the present invention it is preferable to set the passage time of the reaction liquid in the hydrothermal reaction section within the range of 4 to 700 seconds. It is preferable at the point which can manufacture a thing efficiently.
  • the Reynolds number Re of the mixed solution that passes through the piping of the hydrothermal reaction section is set in the range of 1000 to 45000, more preferably in the range of 2000 to 10,000.
  • the vanadium salt aqueous solution and the supercritical or subcritical water can be efficiently and uniformly mixed in the pipe of the hydrothermal reaction section, and the vanadium dioxide-containing particle composition having a narrow particle size distribution. You can get things.
  • a compound that reacts with the vanadium-containing compound is added to a raw material solution containing the vanadium-containing compound and water from the viewpoint of further manifesting the effects of the present invention.
  • the method in which the compound that reacts with the vanadium-containing compound is added to the water in the supercritical or subcritical state can stably express the object effect of the present invention. Is preferable.
  • Embodiment 1 or Embodiment 2 of the present invention the use of a vanadium (IV) -containing compound as the vanadium-containing compound and the use of an alkali as the compound that reacts with the vanadium-containing compound makes it possible to stably monodisperse.
  • This is preferable in that high vanadium dioxide-containing particles can be formed.
  • Embodiment 1 or Embodiment 2 of the present invention a method in which a vanadium (V) -containing compound is used as a vanadium-containing compound and a reducing agent is applied as a compound that reacts with the vanadium-containing compound is also stably performed.
  • Vanadium dioxide-containing particles with high monodispersibility are preferable because they can be formed.
  • the produced vanadium dioxide-containing particles can be prepared as extremely fine particles having an average primary particle size in the range of 1 to 40 nm, and are applied to optical films. When this is done, a highly transparent thermochromic film can be obtained.
  • Embodiment 3 of the present invention it is preferable to use an ultrafiltration device for the desalting treatment for removing the salts from the slurry raw material liquid because the desalting treatment can be performed efficiently.
  • the desalting treatment is performed so that the electrical conductivity after the desalting treatment of the slurry raw material liquid is 1000 ⁇ S / m or less.
  • Vanadium dioxide-containing particles having an average primary particle size and an average crystallite size are preferable in that they can be produced with high accuracy.
  • Embodiment 4 of the present invention it is preferable to adjust the particle size distribution width of the vanadium dioxide-containing particles to 50 nm or less from the viewpoint of improving the haze and ⁇ TSER of the optical film.
  • Embodiment 4 of the present invention from the viewpoint of improving the haze and ⁇ TSER of the optical film, it is preferable to adjust the dispersed particle size after dispersion treatment of the slurry raw material liquid to 300 nm or less.
  • Embodiment 4 of the present invention since the raw material is not damaged (the shape of the raw material is not changed) and can be dispersed, it is preferable to disperse the slurry raw material liquid by high-pressure dispersion treatment.
  • an optical film containing the vanadium dioxide-containing particles can be provided.
  • the present invention has a transparent substrate and an optical functional layer, the optical functional layer contains the vanadium dioxide-containing particles, has a haze of 4% or less, and is at a low temperature (10 ° C.) and a high temperature (70 ° C.).
  • An optical film having a thermal barrier (TSER) difference ⁇ TSER within a range of 5 to 20% is preferable.
  • the optical film of the present invention has a haze of 2% or less, and a thermal barrier (TSER) difference ⁇ TSER between a low temperature (10 ° C.) and a high temperature (70 ° C.) in the range of 10 to 20%. It is preferable that
  • the method for producing vanadium dioxide-containing particles of the present invention uses a flow reactor having a hydrothermal reaction section, a slurry raw material liquid containing at least a vanadium-containing compound and water, a compound that reacts with the vanadium-containing compound, A method for producing vanadium dioxide-containing particles using a reaction liquid mixed with water in a critical or subcritical state, and producing vanadium dioxide-containing particles by a hydrothermal synthesis method, 1) Production condition 1: Method using degassed water subjected to deaeration treatment as water constituting the reaction liquid, 2) Production condition 2: The passage time of the reaction liquid in the hydrothermal reaction section is 3 to 3 3) Manufacturing condition 3: Before the slurry raw material liquid is processed by the hydrothermal synthesis method, a desalting treatment for removing salts from the slurry raw material liquid is performed, and the vanadium dioxide-containing method is performed.
  • the average primary particle size of the particles (hereinafter referred to as “average particle size” or “average particle size”) is in the range of 15 to 40 nm, and the average crystallite size is in the range of 15 to 40 nm. 4) Manufacturing condition 4: Before the step of manufacturing the vanadium dioxide-containing particles, the method includes a step of dispersing the slurry raw material liquid, and the particle size distribution width of the vanadium dioxide-containing particles. Less than 80nm How to integer, by at least one method selected from, characterized in that the production of vanadium dioxide containing particles.
  • vanadium dioxide (VO 2 ) -containing particles is referred to as “vanadium dioxide-containing particles according to the present invention”, “VO 2 -containing particles according to the present invention”, or “vanadium dioxide-containing particles” or “VO 2 -containing particles”. Is also referred to.
  • vanadium-containing compounds are hydrothermally reacted in the presence of supercritical or subcritical degassed water to form vanadium dioxide-containing particles, a “hydrothermal synthesis method”, “hydrothermal reaction”. It is also referred to as “method” or “hydrothermal reaction”, and its implementation step is also referred to as “hydrothermal reaction step”.
  • the “vanadium dioxide (VO 2 ) -containing particles having thermochromic properties” referred to in the present invention means vanadium dioxide-containing particles whose thermochromic properties ( ⁇ T) (%) evaluated by the following method are 20% or more. means.
  • the vanadium dioxide-containing particle dispersion to be measured is filtered with a flow rate of 300 mL / min and a hydraulic pressure of 1 bar (0.1 MPa) using Vivaflow 50 (effective filtration area 50 cm 2 , molecular weight cut-off 5000) manufactured by Sartorius steady.
  • the concentration of the vanadium dioxide-containing particles was adjusted to 10% by mass with respect to the total mass of the polyvinyl alcohol and vanadium dioxide-containing particles in polyvinyl alcohol, and a thickness of 50 ⁇ m manufactured by Teijin DuPont Films Ltd.
  • a measurement film having an optical functional layer with a dry film thickness of 3 ⁇ m is prepared by coating and drying on a polyethylene terephthalate (PET) substrate.
  • thermochromic property ( ⁇ T) (%) is evaluated by the following method.
  • the transmittance (T) at a wavelength of 2000 nm is measured under an environment of 25 ° C./50% RH and 85 ° C./50% RH, and the calculated transmittance difference ( ⁇ T) is measured.
  • ⁇ T (%) is 20% or more, it is determined as a vanadium dioxide (VO 2 ) -containing particle having thermochromic properties.
  • a hydrothermal reaction using water is performed using a flow reactor having a hydrothermal reaction section.
  • the flow reactor according to the present invention is a flow reactor equipped with a hydrothermal reaction section.
  • a hydrothermal reaction part here means the mixing and reactor which implement
  • a raw material liquid containing a vanadium-containing compound and water, and the vanadium-containing is within the range of 4 to 700 seconds, and more preferably within the range of 12 to 700 seconds.
  • the manufacturing condition 1 (embodiment 1)
  • the manufacturing conditions and the details of the flow-type reaction apparatus, constituent materials, and the like applied thereto will be described.
  • the manufacturing condition 2 the manufacturing condition 3
  • the manufacturing condition 4 the description of the configuration common to the manufacturing condition 1 is omitted, and only specific requirements of each manufacturing condition are described.
  • the reaction liquid according to the present invention basically includes 1) a raw material liquid containing a vanadium-containing compound (A) and deaerated water, and 2) a compound (B) that reacts with the vanadium-containing compound. And 3) supercritical or subcritical degassed water, but at least 1) a raw material liquid containing vanadium-containing compound (A) and degassed water, and 3) supercritical or subcritical degassed water
  • a preferred embodiment is a mode in which air and water are divided into structural requirements, and 1) or 3) coexists with 2) a compound (B) that reacts with a vanadium-containing compound.
  • FIG. 1A shows an embodiment 1A suitable for the production condition 1 (embodiment 1) according to the production method of the vanadium dioxide-containing particles of the present invention and FIG. 1B shows a production condition 1 (implementation) according to the production method of the vanadium dioxide-containing particles of the present invention.
  • a manufacturing flow according to preferred embodiment 1B is shown in aspect 1).
  • Embodiment 1A As shown in FIG. 1A, Embodiment 1A, which is one of the production flows applicable to production condition 1, is a raw material containing 1) vanadium-containing compound (A) and degassed water in raw material liquid container 1 (5). 2) A compound (B) that reacts with the vanadium-containing compound, for example, an alkali or a reducing agent dissolved in degassed water at a predetermined concentration, is added to the other raw material liquid container 2 (2) as water. After adding the degassed water to the degassed water in the supercritical or subcritical state under the predetermined temperature and pressure with the heating medium (13), the two are associated at the junction (MP).
  • This is a method for preparing vanadium dioxide-containing particles by preparing a reaction solution and then subjecting it to a hydrothermal treatment in a heating part pipe (17) in a hydrothermal reaction part (16) constituting the hydrothermal reaction part.
  • the embodiment 1B which is one of the production flows applicable to the production condition 1, is a raw material containing 1) a vanadium-containing compound (A) and degassed water in the raw material liquid container 1 (5). 2) Degassed water containing the compound (B) that reacts with the vanadium-containing compound is added to the other raw material liquid container 2 (2), and the compound (B) that reacts with the vanadium-containing compound is added. After the deaerated water contained in the heating medium (13) is degassed in a supercritical or subcritical state at a predetermined temperature and pressure, both are combined at a junction (MP) to form a reaction solution.
  • This is a method for preparing vanadium dioxide-containing particles by performing hydrothermal treatment in the heating part pipe (17) in the hydrothermal reaction part (16) constituting the hydrothermal reaction part.
  • the production condition 1 (embodiment 1) is taken as an example with respect to the overall configuration of the flow-type reaction apparatus having a hydrothermal reaction part commonly applied in the production method (production conditions 1 to 4) of the vanadium dioxide-containing particles of the present invention. Will be described with reference to the drawings.
  • FIG. 2 is a schematic view showing an example of a flow-type reaction apparatus having a hydrothermal reaction section that can be applied to the method for producing vanadium dioxide-containing particles of the present invention.
  • a flow reactor (1) having a hydrothermal reaction section is composed of a raw material liquid containing vanadium-containing compound (A) and a compound (B) that reacts with the vanadium-containing compound and degassed water.
  • Embodiment 1A or a raw material liquid container 1 (5) containing a raw material liquid (Embodiment 1B) containing a vanadium-containing compound (A) and degassed water, supercritical water or subcritical water as the other constituent liquid Degassed water to form (Embodiment 1A), or raw material liquid container 2 (2) containing degassed water (Embodiment 1B) containing a compound (B) that reacts with a vanadium-containing compound, hydrothermal reaction Hydrothermal reaction section (16) having heating medium (14) to be performed, tank (9) for containing reaction liquid after hydrothermal reaction, raw material liquid container 1 (5), raw material liquid container 2 (2) and tank ( 9) and a flow path (pipe, 3 6), the raw material liquid containing at
  • the flow reactor (1) is provided with a cooling part (8) including a flow path (18) for cooling the reaction liquid containing the vanadium dioxide-containing particles after the hydrothermal reaction, if necessary. Also good. Moreover, although mentioned later for details, it mixes with the reaction liquid after the surface modifier, pH adjuster, or hydrothermal reaction added to the reaction liquid containing the vanadium dioxide containing particle
  • a tank (10) for containing a cooling medium (for example, water) for cooling, a surface modifier, a pH adjusting agent, a cooling medium, etc. is sent to the flow path (18) via the flow path (11). You may further have a pump (12) for doing.
  • the flow reactor (1) has a heating medium (13, 15) in the line of the flow path (6) or the flow path (3).
  • the heating medium (13) disposed in the flow path (3) applies degassed water stored in the raw material liquid container 2 (2) to a supercritical water or a predetermined temperature and pressure. Form subcritical water.
  • a hydrothermal reaction section (16) and a heating section in which a raw material liquid containing the vanadium-containing compound (A) and degassed water, a raw material liquid containing the compound (B) and degassed water, and a reaction liquid after the hydrothermal reaction flow.
  • the material of the pipe constituting the pipe (17) and the flow path (3, 6, 11, 18, etc.) is not particularly limited, and examples include stainless steel, aluminum, iron, hastelloy and the like.
  • the line length (L) of the heating section piping of the heating section piping (17) configured inside the hydrothermal reaction section (16) is not particularly limited, and the vanadium-containing compound and vanadium joined at the joining section (MP). It is sufficient that the reaction solution composed of the compound that reacts with the contained compound and water in the supercritical or subcritical state can pass within a time of 3 to 1000 seconds.
  • the speed (flow rate) of the mixed liquid that passes (circulates) the heating part pipe (17) in the hydrothermal reaction part is not particularly limited, but is preferably 0.1 to 10 m / second, more preferably 0.2. ⁇ 8.0 m / sec.
  • the vanadium-containing compound (A) contained in the reaction solution and the compound (B) that reacts with the vanadium-containing compound are water in the presence of deaerated water in a supercritical or subcritical state.
  • the thermal reaction can be effectively carried out under predetermined conditions.
  • the line length (L) of the heating section pipe (17) in the present invention means that each raw material liquid passes through the junction (MP), and after the hydrothermal treatment from the inlet (IN) of the heating medium (14), the heating medium ( 14) The piping part until the outlet (OUT) is reached.
  • the passage time of the reaction liquid in the heating section pipe (17) which is a hydrothermal reaction section is determined by the above-described flow speed of the reaction liquid and the line length (L) of the heating section pipe.
  • the desired conditions can be achieved by controlling the pressure and flow rate according to the liquid feeding pressure of the pumps (4 and 7) installed in each flow path (3 and 6) and the inner diameter of each flow path.
  • the length of the path (18) is not particularly limited, but is generally in the range of 50 to 10000 mm, and preferably in the range of 100 to 1000 mm.
  • the gap of the flow path is not particularly limited, but is generally in the range of 0.1 to 10 mm, and preferably in the range of 1.0 to 8 mm.
  • piping (3, 6, 11, and 18) has the said material, length, and an internal diameter, each may be the same or may differ.
  • the reaction liquid after the hydrothermal reaction obtained by the hydrothermal reaction step is subjected to filtration (for example, ultrafiltration) or centrifugal separation to replace the dispersion medium or solvent, and the vanadium dioxide-containing particles are converted to water or alcohol ( For example, you may wash
  • the obtained vanadium dioxide-containing particles may be dried by any means.
  • TC described in FIG. 2 is a temperature sensor.
  • Hydrothermal reaction step In the hydrothermal reaction step according to the present invention, 1) A reaction liquid obtained by mixing a raw material liquid containing a vanadium-containing compound (A), a compound (B) that reacts with the vanadium-containing compound and deaerated water, and deaerated water in a supercritical or subcritical state (implementation) Aspect 1A) or 2) A raw material liquid containing a vanadium-containing compound (A) and degassed water is mixed with supercritical or subcritical degassed water containing a compound (B) that reacts with the vanadium-containing compound.
  • the resulting reaction solution (Embodiment 1B) Vanadium dioxide-containing particles are obtained by hydrothermal reaction in the presence of supercritical water or subcritical water in a hydrothermal reaction section to which a predetermined temperature and pressure are respectively applied.
  • vanadium-containing compound (A) examples include pentavalent vanadium (hereinafter referred to as vanadium (V)), for example, divanadium pentoxide (V) (V Tetravalent vanadium (hereinafter referred to as vanadium) such as 2 O 5 ), ammonium vanadate (V) (NH 4 VO 3 ), vanadium trichloride (V) (VOCl 3 ), sodium vanadate (V) (NaVO 3 ), etc.
  • V pentavalent vanadium
  • V divanadium pentoxide
  • V Tetravalent vanadium such as 2 O 5
  • V ammonium vanadate
  • V vanadium trichloride
  • V vanadium trichloride
  • V sodium vanadate
  • NaVO 3 sodium vanadate
  • vanadyl oxalate (IV) VOC 2 O 4
  • divanadium tetroxide (IV ) (V 2 O 4 ) dissolved with an acid such as sulfuric acid can be exemplified.
  • said vanadium containing compound may be melt
  • a vanadium containing compound may be used individually by 1 type, or may mix and use 2 or more types. These compounds may be hydrated (hydrate).
  • the compound (B) that reacts with the vanadium-containing compound (A) is not particularly limited as long as it can produce vanadium dioxide-containing particles by hydrothermal reaction of the raw material liquid. Agents and the like.
  • a tetravalent vanadium (IV) -containing compound is used as the ⁇ a> vanadium-containing compound (A)
  • an alkali is applied as the compound (B) that reacts with the vanadium-containing compound (A).
  • the alkali is added to the raw material liquid containing the vanadium-containing compound (A) and water in Embodiment 1, and is added to water for forming supercritical or subcritical water in Embodiment 2.
  • the compound (B) that reacts with the vanadium-containing compound (A) includes a reducing agent (for example, hydrazine and its It is preferable to apply a hydrate or the like.
  • the reducing agent is added to the raw material liquid containing the vanadium-containing compound (A) and water in Embodiment 1, and is added to water for forming supercritical or subcritical water in Embodiment 2. .
  • the water applied to a hydrothermal reaction is deaerated water, It is characterized by the above-mentioned. More specifically, the water constituting the reaction solution containing the vanadium-containing compound (A) that passes through the hydrothermal reaction section and the compound (B) that reacts with the vanadium-containing compound (A) is deaerated water.
  • the deaerated water here is water having an amount of dissolved oxygen at 25 ° C.
  • the deaeration process is a method for removing gas existing in the liquid, for example, oxygen gas or nitrogen gas, etc.
  • the method for preparing deaerated water by the deaeration process is mainly as follows. The methods listed are known.
  • the first method is a vacuum degassing method, which uses a tank, a vacuum degassing tower, or the like to remove gas in the liquid under reduced pressure.
  • a vacuum degassing method which uses a tank, a vacuum degassing tower, or the like to remove gas in the liquid under reduced pressure.
  • degassing is performed. There is a problem that efficiency is low and degassing takes time.
  • the second method is a heating and deaeration method, which is a method of reducing the solubility of dissolved gas, for example, oxygen, and removing it as a gas by increasing the temperature of the target liquid, but requires a lot of thermal energy, In addition, since it is exposed to a high temperature environment, fluctuations in the liquid composition occur.
  • the third method is a chemical method in which a chemical and a gas dissolved in a liquid are reacted and removed, but the gas to be removed is selective and the gas removal efficiency is low.
  • the fourth method is a method using degassed water treated with nitrogen (N 2 ) nanobubbles, and is prepared by mixing (bubbling) nitrogen in water.
  • N 2 nitrogen
  • the fourth method is a method using degassed water treated with nitrogen (N 2 ) nanobubbles, and is prepared by mixing (bubbling) nitrogen in water.
  • the fifth method is a membrane deaeration method in which dissolved oxygen in the liquid is removed by gas permeation through the deaeration membrane.
  • the membrane deaeration method using the deaeration membrane is applied. It is particularly preferable to use the deaerated water because the contact area between the liquid and the gas can be increased, and high deaeration efficiency can be obtained in a small space.
  • the wider the surface (interface) where the liquid and gas are in contact the more efficient the deaeration can be, and the membrane can be degassed by using a hollow fiber, which can dramatically increase the interface. Can be shortened.
  • the hollow fiber membrane is a thin pipe-shaped separation membrane that is used by bundling a plurality.
  • the principle of deaeration using the hollow fiber membrane deaeration module is that the liquid (water) is passed inside the hollow fiber membrane using a pump or gas pressure, and the outside of the hollow fiber membrane is decompressed using a vacuum pump or the like. In this way, bubbles (bubbles), gas (oxygen gas) and the like move to the decompression side through the wall surface of the hollow fiber, and the bubbles and dissolved oxygen concentration in the liquid are reduced.
  • PVDF membrane polyvinylidene fluoride membrane
  • PFA membrane tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer
  • PTFE membrane polytetrafluoroethylene membrane
  • PE membrane polyethylene membrane
  • hollow fiber membrane deaeration modules are commercially available from Mitsubishi Rayon Co., Ltd., DIC Corp., Yokohama Rika Co., Ltd. and the like.
  • a reducing compound may be added as necessary.
  • the compound having reducibility referred to here reacts with the vanadium-containing compound (A) when a pentavalent vanadium (V) -containing compound is used as a vanadium-containing compound (raw material of vanadium dioxide-containing particles) described later.
  • the role of the reducing agent used as compound (B) is clearly different.
  • the reducing agent used in the above method is used in the range of 1.01-1.50 mol per 1 mol of the vanadium (V) -containing compound.
  • the addition amount of the compound having is preferably in the range of 0.05 to 1.0 mass% with respect to the deaerated water.
  • the system to be used is the raw material liquid container 1 storing the vanadium-containing compound (A) and the compound (B) or the raw material container 2 storing deaerated water.
  • the raw material liquid container 1 storing the vanadium-containing compound (A) and the raw material container 2 storing deaerated water containing the compound (B) can also be added. Can be added.
  • the effective use of the reducing compound in the present invention is to use a moderately dissolved oxygen concentration of deaerated water without excessively reducing the dissolved oxygen concentration of the deaerated water.
  • the load of production conditions can be reduced, and vanadium dioxide (VO 2 ) having a target valence can be more stably produced during a hydrothermal reaction.
  • the reducing compound that can be used for supporting deaerated water is not particularly limited, and examples thereof include oxalic acid and its hydrate, formic acid and its hydrate, hydrazine (N 2 H 4 ), and Its hydrate (N 2 H 4 ⁇ H 2 O), water-soluble vitamins such as ascorbic acid and its derivatives, sodium erythorbate, BHT (dibutylhydroxytoluene), BHA (butylhydroxyanisole), propyl gallate, sulfite Examples thereof include antioxidants such as sodium and reducing sugars such as glucose, fructose, glyceraldehyde, lactose and maltose. As described above, the addition amount of the reducing compound is in the range of 0.05 to 1.0% by mass, preferably in the range of 0.10 to 0.5% by mass with respect to the deaerated water. It is.
  • the vanadium (IV) -containing compound (raw material of vanadium dioxide-containing particles) applied to the item ⁇ a> described in (1)
  • Hydrothermal reaction step is not particularly limited, and includes the vanadium-containing compounds listed above. It can select suitably from a compound (A). Among them, vanadium oxide sulfate (IV) (VOSO 4 ) is preferable from the viewpoint of generating as little by-products as possible after the hydrothermal reaction.
  • a vanadium (IV) containing compound may be used individually by 1 type, or may mix and use 2 or more types.
  • the initial concentration of the vanadium (IV) -containing compound contained in the reaction solution is not particularly limited as long as the objective effect of the present invention is obtained, but is preferably 0.1 to 1000 mmol / L. With such a concentration, the vanadium (IV) -containing compound is sufficiently dissolved or dispersed, the average particle size (particle size) of the resulting vanadium dioxide-containing particles is reduced, and the particle size (particle size) distribution is narrowed. Thus, the thermochromic properties of the vanadium dioxide-containing particles and the transparency of the optical film containing the vanadium dioxide-containing particles can be further enhanced.
  • the initial concentration of the vanadium (IV) compound contained in the reaction solution is the average particle size and particle size distribution of the vanadium dioxide-containing particles, that is, the thermochromic properties of the vanadium dioxide-containing particles, and the transparency of the optical film containing the vanadium dioxide-containing particles. In view of the above, it is more preferably in the range of 20 to 600 mmol / L, and still more preferably in the range of 50 to 400 mmol / L.
  • the above “initial concentration” is the amount of vanadium (IV) -containing compound in 1 L of the reaction liquid before hydrothermal reaction (the total amount when two or more vanadium (IV) -containing compounds are included). is there.
  • the compound (B) that reacts with the vanadium-containing compound (A) that can be used together with the vanadium (IV) -containing compound as described in the item (a) in the (1) hydrothermal reaction step is an alkali.
  • the vanadium-containing compound (A) is a vanadium (IV) -containing compound
  • the compound (B) that reacts with the vanadium-containing compound is at least It is preferable to use a reaction solution containing one kind of alkali.
  • the compound (B) that reacts with the vanadium-containing compound is composed only of an alkali.
  • the alkali in the present invention means a substance that generates hydroxide ions (OH ⁇ ) in an aqueous solution.
  • the alkali ions themselves This includes chemical compounds that do not result in the formation of hydroxide ions.
  • the alkali is not particularly limited, and examples thereof include ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate.
  • the said alkali can be used individually by 1 type or in combination of 2 or more types.
  • ammonia, sodium hydroxide, or potassium hydroxide is preferable, ammonia or sodium hydroxide is more preferable, and ammonia is more preferable.
  • the alkali concentration in the raw material liquid composed of alkali and degassed water is not particularly limited, but is preferably in the range of 0.01 to 10 mol / L, for example, 0.1 to 5 mol / L. More preferably within the range.
  • the amount of alkali in the reaction liquid obtained by mixing each raw material liquid is not particularly limited.
  • vanadium-containing compound (A), compound (B) that reacts with vanadium-containing compound, and supercritical As the pH of the reaction solution composed of degassed water in the critical state, it is preferable to add an amount in the range of 6.8 to 7.2, and an amount in the range of 6.9 to 7.1. It is more preferable to add.
  • the vanadium (V) containing compound (raw material of vanadium dioxide containing particle
  • the initial concentration of the vanadium (V) -containing compound contained in the reaction solution is not particularly limited as long as the objective effect of the present invention is obtained, but is preferably in the range of 0.1 to 1000 mmol / L. If it is such a density
  • the initial concentration of the vanadium (V) compound contained in the reaction solution is the particle size and particle size distribution of the vanadium dioxide-containing particles, that is, the thermochromic properties of the vanadium dioxide-containing particles and the transparency of the optical film containing the vanadium dioxide-containing particles.
  • said "initial concentration" is the amount of vanadium (V) containing compounds in 1 L of reaction liquid before the hydrothermal reaction (the total amount when two or more vanadium (V) containing compounds are included). is there.
  • ⁇ Compound (B) -2 Reducing agent>
  • the compound (B) that reacts with the vanadium-containing compound used together with the vanadium (V) -containing compound is a reducing agent. It is preferable.
  • the reducing agent examples include water solutions such as oxalic acid and its hydrate, formic acid and its hydrate, hydrazine (N 2 H 4 ) and its hydrate (N 2 H 4 .H 2 O), ascorbic acid and the like.
  • Vitamins and their derivatives sodium erythorbate, BHT (dibutylhydroxytoluene), BHA (butylhydroxyanisole), propyl gallate, sodium sulfite, and other antioxidants, glucose, fructose, glyceraldehyde, lactose, maltose, etc.
  • a reducing sugar can be exemplified.
  • the said reducing agent can be used individually by 1 type or in combination of 2 or more types.
  • hydrazine or a hydrate thereof is preferable. That is, the hydrothermal reaction is preferably performed in a reaction solution in which the compound (B) that reacts with the vanadium (V) -containing compound (A) contains at least one of hydrazine and its hydrate. Furthermore, it is more preferable that the compound that reacts with the vanadium-containing compound is only one of hydrazine and its hydrate.
  • the amount of the reducing agent in the reaction liquid obtained by mixing each raw material liquid is determined considering the pH during the reaction and the amount decomposed during the reaction with respect to the vanadium (V) -containing compound (A). It is preferable to add more than mol.
  • the amount of the reducing agent is more preferably in the range of about 1.01 to 1.50 mol, more preferably in the range of 1.05 to 1.30 mol, with respect to 1 mol of the vanadium (V) -containing compound. More preferably it is.
  • vanadium pentoxide (V) V 2 O 5
  • the vanadium-containing compound By adding hydrogen peroxide, the vanadium-containing compound can be uniformly dissolved.
  • the vanadium-containing compound may be pretreated in the presence of hydrogen peroxide or a reducing agent before the hydrothermal reaction.
  • hydrogen peroxide and a reducing agent are sequentially added, for example, within a temperature range of 20 to 40 ° C., with stirring as necessary. The reaction can be carried out for about 0.5 to 10 hours.
  • the pH of the reaction liquid obtained by mixing the raw material liquids varies depending on the vanadium (V) -containing compound used, and is preferably adjusted to the desired pH depending on the amount of reducing agent added.
  • V vanadium
  • reducing agent added for example, in the case of ammonium vanadate (NH 4 VO 3 ), it is preferable to add an amount such that the pH is within the range of 8.0 to 11.0, and an amount within the range of 9.0 to 10.0. It is more preferable to add.
  • vanadium pentoxide or vanadium trichloride oxide it is preferable to add an amount such that the pH is in the range of 3.5 to 5.5, and an amount in the range of 4.0 to 5.0. It is more preferable to add.
  • phase transition regulator of vanadium dioxide-containing particles In the method for producing vanadium dioxide-containing particles of the present invention, in the hydrothermal reaction section, the phase transition regulator containing a specific element is used to adjust the phase transition temperature of the vanadium-containing compound contained in the reaction liquid to the vanadium dioxide-containing particles. Can be contained.
  • the method of adding the phase transition modifier to the reaction solution is not particularly limited, and a known method can be used.
  • a known method can be used as an addition method to the reaction solution.
  • the method of adding directly to the reaction liquid before a hydrothermal reaction can also be used.
  • the phase transition regulator is not particularly limited, but for example, tungsten, titanium, molybdenum, niobium, tantalum, tin, rhenium, iridium, osmium, ruthenium, germanium, chromium, iron, gallium, aluminum, fluorine, phosphorus
  • a material containing a metal element other than vanadium can be used.
  • the reaction solution contains the phase transition regulator, the phase transition temperature of the obtained vanadium dioxide-containing particles can be lowered.
  • the addition amount of the phase transition regulator is not particularly limited, but the element ratio (atomic ratio) between vanadium contained in the vanadium-containing compound and the metal element (excluding vanadium) contained in the phase transition regulator is not limited.
  • phase transition regulator is not particularly limited, but examples thereof include oxides and ammonium salts of the above metal elements (except vanadium).
  • phase Examples of transition modifiers can include, for example, ammonium tungstate para pentahydrate ((NH 4) 10 W 12 O 41 ⁇ 5H 2 O) and the like.
  • hydrothermal reaction in the method for producing vanadium dioxide-containing particles of the present invention, in the hydrothermal reaction step, the reaction solution is hydrothermally reacted to form vanadium dioxide-containing particles.
  • hydrothermal reaction as used herein means a mineral synthesis or alteration reaction, that is, a chemical reaction performed in the presence of high-temperature water, particularly high-temperature and high-pressure water.
  • the hydrothermal reaction in the present invention is performed in a state where the temperature is 150 ° C. or higher and the pressure is higher than the saturated vapor pressure, that is, the deaerated water exists in a supercritical or subcritical state. It is characterized by. It is known that by performing the reaction under such high-temperature and high-pressure conditions, a unique reaction occurs due to the presence of degassed water, unlike the case of normal pressure and high temperature where almost no degassed water can exist. Yes. It is also known that the solubility of oxides such as silica and alumina is improved and the reaction rate is improved.
  • the average particle diameter (D) of the formed vanadium dioxide-containing particles and the particle size distribution can be narrowed, and the vanadium dioxide containing
  • the thermochromic property of the particles and the transparency of the optical film containing the vanadium dioxide-containing particles can be improved (decrease in haze).
  • Hydrothermal reaction conditions are not particularly limited as long as the temperature at which water is present in a supercritical or subcritical state is 150 ° C. or higher and the pressure is above the saturated vapor pressure, and other conditions (for example, , The amount of the reaction product, the reaction temperature, the reaction pressure, the reaction time, etc.).
  • the saturated water vapor pressures at 150 ° C., 250 ° C., 270 ° C., and 350 ° C. are 0.48 MPa, 3.98 MPa, 5.51 MPa, and 16.54 MPa, respectively.
  • the temperature is 374.15 ° C. or higher and the pressure is 22.12 MPa or higher, the water is in a supercritical state.
  • the temperature and pressure conditions in the hydrothermal reaction are not particularly limited as long as they are in the range of 150 to 500 ° C. as described above and the pressure is higher than the saturated vapor pressure. It is more preferable that the pressure is in the range of 500 ° C., the pressure is in the range of 10 to 40 MPa, and the pressure is higher than the saturated vapor pressure at the set temperature.
  • the temperature is 300 ° C. or higher, the average particle diameter (D) and the like can be further reduced. Further, when the temperature is 500 ° C. or lower, the thermochromic property is not lowered due to the average particle size (D) being too small.
  • the temperature is in the range of 350 to 450 ° C.
  • the pressure is in the range of 20 to 40 MPa
  • the pressure is higher than the saturated vapor pressure at the set temperature
  • the hydrothermal reaction is performed in the presence of supercritical water having a temperature in the range of 380 to 400 ° C. and a pressure in the range of 25 to 30 MPa.
  • the hydrothermal reaction time is not particularly limited, and arbitrary conditions can be selected.
  • Examples of the surface modifier that can be provided in the present invention include organic silicon compounds, organic titanium compounds, organic aluminum compounds, organic zirconia compounds, surfactants, and silicone oils.
  • the number of reactive groups in the surface modifier is not particularly limited, but is preferably 1 or 2.
  • organosilicon compounds such as hexamethyldisilazane, trimethylethoxysilane, trimethylmethoxysilane, tetraethoxysilane (tetraethyl orthosilicate), trimethylsilyl.
  • Chloride methyltriethoxysilane, dimethyldiethoxysilane, decyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3- Aminopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 3-glycidoxypropyl methyldimethoxysilane, and the like.
  • an organosilicon compound can also be obtained as a commercial item, for example, SZ 6187 (made by Toray Dow Corning) etc. can be used conveniently.
  • organosilicon compounds it is preferable to use an organic silicate compound having a low molecular weight and high durability, and in particular, hexamethyldisilazane, tetraethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, and trimethylsilyl chloride are used. Is more preferable.
  • Organic titanium compound examples include tetrabutyl titanate, tetraoctyl titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, and bis (dioctyl pyrophosphate) oxy Acetate titanate, as chelate compound, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethyl acetoacetate, titanium phosphate compound, titanium octylene glycolate, titanium ethyl acetoacetate, titanium lactate ammonium salt, titanium lactate, titanium triethanol Examples include aminates. Moreover, an organic titanium compound can also be obtained as a commercial item, for example, Preneact TTS, Preneact TTS44 (above
  • Organoaluminum compound examples include aluminum isopropoxide, aluminum tert-butoxide and the like.
  • Organic zirconia compound examples include normal propyl zirconate, normal butyl zirconate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium tetraacetylacetonate and the like.
  • a surfactant is a compound having a hydrophilic group and a hydrophobic group in the same molecule.
  • the hydrophilic group of the surfactant include a hydroxy group, a hydroxyalkyl group having 1 or more carbon atoms, a carbonyl group, an ester group, an amino group, an amide group, an ammonium salt, a thiol, a sulfonate, and a phosphate.
  • a polyalkylene glycol group a polyalkylene glycol group.
  • the amino group may be primary, secondary, or tertiary.
  • Specific examples of the hydrophobic group of the surfactant include an alkyl group, a silyl group having an alkyl group, and a fluoroalkyl group.
  • the alkyl group may have an aromatic ring as a substituent.
  • the surfactant only needs to have at least one hydrophilic group and one hydrophobic group as described above in the same molecule, and may have two or more groups. More specifically, as the surfactant, myristyl diethanolamine, 2-hydroxyethyl-2-hydroxydodecylamine, 2-hydroxyethyl-2-hydroxytridecylamine, 2-hydroxyethyl-2-hydroxytetra Decylamine, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, di-2-hydroxyethyl-2-hydroxydodecylamine, alkyl (8 to 18 carbon atoms) benzyldimethylammonium chloride, ethylenebisalkyl (C8-18) Amide, stearyl diethanolamide, lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide,
  • silicone oil examples include straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, carrubinol-modified silicone oil, and methacryl-modified. Silicone oil, mercapto modified silicone oil, different functional group modified silicone oil, polyether modified silicone oil, methylstyryl modified silicone oil, hydrophilic special modified silicone oil, higher alkoxy modified silicone oil, higher fatty acid-containing modified silicone oil and fluorine modified silicone And modified silicone oil.
  • straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil
  • amino-modified silicone oil amino-modified silicone oil
  • epoxy-modified silicone oil epoxy-modified silicone oil
  • carboxyl-modified silicone oil carboxyl-modified silicone oil
  • carrubinol-modified silicone oil examples include methacryl-modified.
  • silicone oil examples include straight silicone oil such as dimethyl silicone oil,
  • the surface modifier is appropriately diluted with hexane, toluene, methanol, ethanol, acetone, water or the like and mixed with the reaction solution after the hydrothermal reaction in the form of a solution.
  • the number of carbon atoms in the organic functional group introduced by the surface modifier is preferably 1-6. Thereby, durability can be improved.
  • the solution containing the surface modifier may be adjusted to an appropriate pH value (for example, 2 to 12) using a pH adjuster.
  • limit especially as a pH adjuster The thing similar to the below-mentioned pH adjuster can be used.
  • the addition amount of the surface modifier in the case of using the surface modifier is not particularly limited, but is in the range of 0.1 to 100% by mass with respect to the mass of the vanadium dioxide-containing particles obtained by the hydrothermal reaction.
  • the content is preferably in the range of 1 to 10% by mass.
  • the addition of the surface modifier is preferably started immediately after the hydrothermal reaction (immediately after the end of the reaction) from the viewpoint of modifying the surface of the vanadium dioxide-containing particles. Specifically, the addition is preferably performed within 10 seconds from the end of the reaction, and more preferably within 5 seconds.
  • the method for adding the surface modifier is not particularly limited, and a known method can be used.
  • the surface modifier or a solution containing the surface modifier
  • the surface modifier is pumped from the tank (10) to the reaction solution immediately after the hydrothermal reaction. It can mix with a reaction liquid by making it join a heating part piping (17) via a flow path (11) by (12).
  • the speed (flow speed) at which the solution containing the surface modifier passes (flows) through the flow path (11) is not particularly limited, but is preferably in the range of 0.01 to 10 mL / second, more preferably 0.8. Within the range of 1-5 mL / sec.
  • the surface modifier and the vanadium dioxide-containing particles are sufficiently brought into contact with each other, and the effect of the surface modifier (particle aggregation suppressing effect, Dispersion stability and storage stability) can be effectively exhibited.
  • the mixing position of the reaction liquid and the surface modifier after the hydrothermal reaction (installation position of the pipe 11) is not particularly limited, but in order to start the addition of the surface modifier immediately after the hydrothermal reaction, the hydrothermal reaction section ( It is preferable to arrange it immediately after the outlet (B) of 16). Further, when the cooling unit (8) is provided after the hydrothermal reaction unit (16) as in the flow reactor (1), it is immediately after the hydrothermal reaction unit (16) as shown in FIG. It is preferable to arrange it before the cooling section (8).
  • the separate line comprised by a tank (10), a flow path (11), and a pump (12) is provided separately. May be.
  • the flow path (11) is further connected to the reaction liquid immediately after the hydrothermal reaction from the tank (10).
  • a pH adjuster can be added via.
  • organic or inorganic acids or alkalis such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid (including hydrate), ammonium hydroxide, ammonia, etc. are used. Can do.
  • the pH of the reaction solution after the hydrothermal reaction is 3.0 from the viewpoint of the particle size of the vanadium dioxide-containing particles, the particle size distribution, the thermochromic properties of the vanadium dioxide-containing particles, and the transparency of the optical film containing the vanadium dioxide-containing particles. Is preferably in the range of ⁇ 9.0, more preferably in the range of 4.0 to 7.0.
  • the pH adjuster may be the same as or different from the alkali and reducing agent used as the compound that reacts with the vanadium-containing compound in the hydrothermal reaction.
  • the pH adjusting agent is appropriately diluted with methanol, ethanol, water or the like and mixed with the reaction solution after the hydrothermal reaction in the form of a solution.
  • the method for adding the pH adjuster is not particularly limited, and a known method can be used.
  • a pH adjusting agent or a solution containing the pH adjusting agent
  • a pH adjusting agent is pumped from the tank (10) to the reaction liquid immediately after the hydrothermal reaction. It can be mixed with the reaction solution via the flow path (11) in (12).
  • the mixing position of the reaction solution after the hydrothermal reaction and the pH adjuster is not particularly limited, but from the viewpoint of starting the addition of the surface modifier after the hydrothermal reaction, It is preferable to dispose after the thermal reaction section (16).
  • the cooling unit (16) is provided after the hydrothermal reaction unit (16). It may be arranged before 8), or after the cooling section (8) and before the tank (9).
  • the supply line comprised from a tank (10), a flow path (11), and a pump (12) is respectively It may be provided individually.
  • the method of mixing a pH adjuster and a surface modifier, or a pH adjuster and a cooling medium, and supplying with one supply line may be sufficient.
  • Cooling step In the method for producing vanadium dioxide-containing particles of the present invention, [1] In addition to the hydrothermal reaction step, cooling for cooling the reaction solution after the hydrothermal reaction (a dispersion containing vanadium dioxide-containing particles). It is preferable to further have a process (cooling part (8) shown in FIG. 2).
  • the cooling step it is preferable to start cooling the reaction liquid after the hydrothermal reaction within 1 minute after the hydrothermal reaction is performed for a predetermined time (at the end of the reaction), but the entire reaction liquid is cooled within this time. If this is difficult, the reaction solution may be cooled sequentially by a predetermined amount while maintaining the reaction temperature at the reaction temperature with a wide reaction time.
  • the cooling rate can be adjusted as appropriate.
  • the method for cooling the reaction solution after the hydrothermal reaction is not particularly limited, and can be applied in the same manner as in a known method, or appropriately changed.
  • a cooling method for example, a method of immersing the reaction solution after the hydrothermal reaction in a cooling medium while stirring if necessary, a method of mixing the reaction solution after the hydrothermal reaction and the cooling medium (particularly water), Examples thereof include a method in which a gaseous cooling medium (for example, liquid nitrogen) is passed through the reaction solution after the hydrothermal reaction.
  • a gaseous cooling medium for example, liquid nitrogen
  • a method of bringing the reaction solution after the hydrothermal reaction and the cooling medium into contact with each other through a pipe is preferable as illustrated in FIG.
  • the cooling is performed using the cooling section (8) connected to the hydrothermal reaction section (16) directly or via other components. Is preferred.
  • cooling section (8) connected to the hydrothermal reaction section (16) and having a flow path (18) inside in the flow reaction apparatus (1)
  • the cooling method which can be used for this invention is not limited to the form demonstrated below.
  • the cooling method according to the present invention it is preferable to cool the reaction liquid after the hydrothermal reaction by passing (circulating) the flow path (18) of the flow reactor (1). That is, the flow-type reaction apparatus (1) shown in FIG. 2 will be described as an example.
  • the reaction liquid containing vanadium dioxide-containing particles is passed downstream of the hydrothermal reaction section (16). ) Is allowed to pass (circulate).
  • the cooling medium (C) flows into the cooling section (8), and the flow path (18) is cooled from the outer surface.
  • the tank (10) is modified as described above in the flow reactor (1) as described above.
  • the cooling medium may be added directly.
  • the cooling medium may be used as a cooling medium having a pH adjusting effect when the pH adjusting agent is dissolved in water or the like as the medium.
  • the mixing ratio of the cooling medium with the reaction liquid after the hydrothermal reaction is not particularly limited as long as a desired cooling rate can be achieved.
  • the mixing ratio can be controlled by setting the flow rate of the reaction liquid and the cooling medium after the hydrothermal reaction so as to be the ratio as described above.
  • the temperature of the cooling medium is not particularly limited, but is preferably higher than the phase transition temperature (about 68 ° C.) of vanadium dioxide, and more preferably 70 to 95 ° C.
  • the temperature of the mixture of the reaction liquid and water immediately after the hydrothermal reaction is maintained at 70 to 95 ° C. for 5 minutes or longer after the reaction liquid after the hydrothermal reaction is mixed with water. More preferably.
  • the purity of the desired rutile-type crystal phase (R phase) vanadium dioxide can be further improved.
  • the upper limit of the time for maintaining the temperature of the mixture of the reaction liquid immediately after the hydrothermal reaction and water is not particularly limited, but it is sufficient if it is 10 minutes or less after mixing the reactant immediately after the hydrothermal reaction with water. It is.
  • the pH of the mixture of the reaction solution after the hydrothermal reaction and the cooling medium is not particularly limited, but may be in the range of 4.0 to 7.0. preferable.
  • the stability of the vanadium dioxide-containing particles after particle formation can be improved. Therefore, the purity of vanadium dioxide of the desired rutile type crystal phase (R phase) can be further improved, and the thermochromic properties of the vanadium dioxide-containing particles can be more effectively improved.
  • the means for achieving such a pH value is not particularly limited, and may be achieved by adding the aforementioned pH adjuster to the reaction solution after the hydrothermal reaction before the cooling step. It may be achieved by using a cooling medium mixed with a modifier.
  • the mixing position of the reaction liquid after the hydrothermal reaction and the cooling medium (installation position of the pipe 11) is not particularly limited, but considering the cooling efficiency of the reaction liquid after the hydrothermal reaction, etc.
  • the pipe (11) is preferably connected to the heating section pipe (17) at a position 10 to 500 mm away from the outlet on the tank (9) side.
  • the cooled reaction liquid (cooling liquid) after the hydrothermal reaction is stored in the tank (9) via the control valve (19).
  • the dispersion medium or solvent may be replaced by filtration (for example, ultrafiltration) or centrifugation, and the vanadium dioxide-containing particles may be washed with water, alcohol (for example, ethanol), or the like.
  • the obtained vanadium dioxide-containing particles may be dried by any means.
  • Embodiment 2 using a flow reactor having a hydrothermal reaction section, after preparing a slurry raw material liquid containing at least a vanadium-containing compound and water, and a compound that reacts with the vanadium-containing compound, the reaction liquid is used.
  • the hydrothermal reaction section that performs hydrothermal synthesis that constitutes the flow reactor the hydrothermal reaction is performed within a passage time of 3 to 1000 seconds.
  • the average particle diameter (D) and polydispersity index (PDI) values of the vanadium dioxide-containing particles are extremely small by carrying out in the presence of supercritical or subcritical water under high pressure.
  • excellent thermochromic properties of vanadium dioxide-containing particles and transparency of an optical film including vanadium dioxide-containing particles can be achieved. This is because the hydrothermal reaction is carried out under high pressure in the presence of supercritical or subcritical water to complete the liquid mixing and reaction in a very short time, and the precipitated vanadium dioxide microcrystals are formed. It is presumed that sufficient time for large crystal growth is not given.
  • the vanadium-containing compound in the hydrothermal reaction section that performs hydrothermal synthesis of the flow reactor and The transit time of the reaction liquid obtained by mixing the raw material liquid containing water, the compound that reacts with the vanadium-containing compound, and water in a supercritical or subcritical state is within a range of 3 to 1000 seconds, By satisfying these conditions, the vanadium dioxide-containing particles can be more reliably formed, preferably in the range of 4 to 700 seconds, and more preferably in the range of 12 to 700 seconds.
  • the reaction liquid in the production condition 2 basically includes 1) a raw material liquid containing a vanadium-containing compound (A) and water, 2) a compound (B) that reacts with the vanadium-containing compound, and 3) It is composed of supercritical or subcritical water, but is divided into at least 1) a raw material liquid containing the vanadium-containing compound (A) and water, and 3) supercritical or subcritical water.
  • a mode in which 1) or 3) and 2) a compound (B) that reacts with a vanadium-containing compound coexists is a preferred embodiment.
  • FIG. 3A shows embodiment 2A suitable for production condition 2 (embodiment 2) relating to the method for producing vanadium dioxide-containing particles of the present invention
  • FIG. 2 shows a manufacturing flow according to preferred embodiment 2B.
  • Embodiment 2A In Embodiment 2A, as shown in FIG. 3A, in the raw material liquid container 1 (5), 1) a raw material liquid containing a vanadium-containing compound (A) and water, and 2) a compound (B) that reacts with the vanadium-containing compound, For example, an alkali or a reducing agent is added, ion-exchanged water is added as water to the other raw material liquid container 2 (2), and the ion-exchanged water is supercritical at a predetermined temperature and pressure with a heating medium (13).
  • a raw material liquid containing a vanadium-containing compound (A) and water for example, an alkali or a reducing agent is added, ion-exchanged water is added as water to the other raw material liquid container 2 (2), and the ion-exchanged water is supercritical at a predetermined temperature and pressure with a heating medium (13).
  • a raw material liquid containing vanadium-containing compound (A) and water is added to raw material liquid container 1 (5), and the other raw material liquid container 2 (2) is added.
  • Ion exchange water containing a compound (B) that reacts with a vanadium-containing compound is added, and the ion exchange water containing the compound (B) that reacts with the vanadium-containing compound is heated at a predetermined temperature with a heating medium (13), After making water in a supercritical or subcritical state under pressure, the two are combined at a junction (MP) to form a reaction solution, and then heated in the hydrothermal reaction section (16) constituting the hydrothermal reaction section.
  • MP junction
  • the hydrothermal reaction shown in FIG. As an example of the flow-type reaction apparatus applied in the production condition 2 (embodiment 2) relating to the production method of the vanadium dioxide-containing particles of the present invention described above, the hydrothermal reaction shown in FIG.
  • the flow-type reaction apparatus provided with a section can be similarly applied, and the detailed description thereof is omitted. Details of the hydrothermal reaction process configuration and hydrothermal reaction conditions (temperature / pressure), heating section piping, cooling process, etc. of the flow reactor equipped with the hydrothermal reaction section are described in the manufacturing conditions 1. Can be applied according to the contents.
  • the Reynolds number Re in the present invention complies with the following definition.
  • D 1 (m) is the equivalent circular diameter of the internal flow path of the heating section pipe (17) of the hydrothermal reaction section through which the mixed liquid passes
  • U is the linear velocity (m / s) of the mixed liquid in the internal flow path
  • the mixed liquid When the density (kg / m 3) [rho, viscosity coefficient of the mixture (Pa ⁇ s) and eta, the Reynolds number Re of the mixture is determined by a dimensionless number determined by the following equation (1).
  • Re D 1 U ⁇ / ⁇
  • laminar flow a region where Re is less than 2300
  • transition region a region where 2300 ⁇ Re ⁇ 3000 is referred to as a transition region
  • Re exceeds 3000 a region where Re exceeds 3000 is referred to as turbulent flow.
  • the liquid feeding pressure and heating of the pumps (4, 7) installed in the respective channels (3, 6) It can be controlled by appropriately setting conditions such as the control valve (19) for controlling the inner diameter, pressure and flow rate of the partial pipe (17).
  • the vanadium dioxide-containing particles are subjected to a hydrothermal reaction within a range of 3 to 1000 seconds in the presence of supercritical water or subcritical water in a hydrothermal reaction section to which a predetermined temperature and pressure are respectively applied. Is obtained.
  • the applicable vanadium-containing compound (A) As the applicable vanadium-containing compound (A), the compound described in detail in the above-described production condition 1 (embodiment 1) can be applied.
  • a tetravalent vanadium (IV) -containing compound an alkali which is a compound (B) that reacts with the vanadium-containing compound (A), or a pentavalent vanadium (V) -containing compound, and a reaction with the vanadium-containing compound (A).
  • the reducing agent or the like which is the compound (B) to be used the compound whose details are described in the explanation of the production condition 1 (embodiment 1) can be applied.
  • Water used in the reaction solution Water used in the reaction solution
  • Water for dissolving the vanadium-containing compound, water for dissolving the compound that reacts with the vanadium-containing compound, and water used for making the supercritical water or the subcritical water are preferably those with less impurities, particularly limited. water but are not, for example, distilled water, ion exchange water, pure water, the use of ultrapure water, nitrogen (N 2) nano bubbles treated water or the like which is preferably nitrogen (N 2) nano bubble treatment More preferably, is used.
  • nitrogen (N 2 ) nanobubble-treated water (N 2 nanobubble-treated water) is prepared by mixing (bubbling) nitrogen in water.
  • the dissolved oxygen concentration of the water is lowered, so that the resulting vanadium dioxide-containing particles are suppressed / prevented from being oxidized again, and the resulting vanadium dioxide content is obtained.
  • the particle size of the particles can be made smaller and the particle size distribution can be made narrower (polydispersity index is made smaller).
  • the dissolved oxygen concentration of the water treated with nitrogen (N 2 ) nanobubbles is not particularly limited, but it is preferably 2 mg / L or less, preferably 1 mg / L or less (lower limit: 0 mg / L).
  • the water contained in the reaction liquid is water that has been subjected to nitrogen (N 2 ) nanobubble treatment
  • water contained in the raw material liquid containing the vanadium-containing compound and water, or a compound that reacts with the vanadium-containing compound and water are included.
  • at least one of the water contained in the raw material liquid is nitrogen (N 2 ) nanobubble-treated water, so that the water contained in the reaction solution is nitrogen (N 2 ) nanobubble-treated water.
  • Various additives In the production condition 2 according to the present invention, conventionally known various additives can be applied. For example, vanadium dioxide-containing particle phase transition regulators, surface modifiers (organosilicon compounds, organotitanium compounds, organoaluminum compounds) , Organic zirconia compounds, surfactants, silicone oils, etc.), pH adjusters, and the like. Specific compounds of these various additives are described in the description of production condition 1 (embodiment 1). The compounds described in detail can be applied.
  • Production condition 3 embodiment 3
  • a flow reactor having a hydrothermal reaction section, a slurry raw material liquid containing at least a vanadium-containing compound and water, and a compound that reacts with the vanadium-containing compound
  • a method for producing vanadium dioxide-containing particles by using a reaction liquid obtained by mixing water in a supercritical or subcritical state, and producing vanadium dioxide-containing particles by a hydrothermal synthesis method.
  • the average primary particle size of the vanadium dioxide-containing particles produced by the hydrothermal synthesis method is in the range of 15 to 40 nm, and the average The crystallite diameter is adjusted to be within a range of 15 to 40 nm.
  • FIG. 4 is a process flow diagram showing an example of a production process of production condition 3 for vanadium dioxide-containing particles having a desalting treatment process.
  • the slurry raw material liquid according to the present invention includes (1) a vanadium-containing compound, (2) a compound that reacts with the vanadium-containing compound (for example, alkali), and (3) ion-exchanged water as main components.
  • various additives are added as necessary.
  • the prepared slurry raw material liquid is desalted to remove unnecessary salts (for example, ammonium ions, sulfate ions, sodium ions, potassium ions, calcium ions, etc.) from the slurry raw material liquid, and the slurry raw material liquid Is a step of adjusting the electrical conductivity of the resin to 1000 ⁇ S / m or less.
  • the applicable desalting treatment method is not particularly limited, and examples thereof include a decantation method, a centrifugal separation method, and an ultrafiltration method. Among them, the ultrafiltration method is particularly preferable.
  • the electrical conductivity of the slurry raw material liquid is preferably in the range of 50 to 1000 ⁇ S / m, more preferably in the range of 100 to 800 ⁇ S / m.
  • the electrical conductivity can be easily measured using a commercially available electrical conductivity meter.
  • a “reaction liquid” is prepared by associating the slurry raw material liquid subjected to the desalting treatment with the supercritical or subcritical ion exchange water, and then a hydrothermal reactor (for example, distribution And a vanadium dioxide-containing particle having an average primary particle size in the range of 15 to 40 nm and an average crystallite size in the range of 15 to 40 nm.
  • a hydrothermal reactor for example, distribution And a vanadium dioxide-containing particle having an average primary particle size in the range of 15 to 40 nm and an average crystallite size in the range of 15 to 40 nm.
  • the production condition 3 according to the present invention is characterized in that before the vanadium dioxide-containing particles are formed by a hydrothermal synthesis method, a desalting treatment for removing a predetermined amount of salts is performed on the prepared slurry raw material liquid. .
  • the desalting treatment means is not particularly limited as long as it is a method capable of removing a predetermined concentration of salts such as ammonium ions, sulfate ions, sodium ions, potassium ions, calcium ions from the slurry raw material liquid.
  • An application method, a centrifugal separation method, an ultrafiltration method, and the like can be applied, and among these, an ultrafiltration method is particularly preferable.
  • ⁇ Centrifuge method> In the centrifugation method applicable to the desalting treatment of the second step, the prepared slurry raw material liquid is separated into a solid phase and a liquid phase by a centrifuge, and then an aqueous phase containing unnecessary salts is separated. A part of the liquid is discharged out of the system by the decantation method, and then the same amount of ion-exchanged water as the discharged separated liquid is added to the desalted slurry raw material liquid, and then dispersed. By repeating this operation, unnecessary salts are discharged out of the system, and the slurry raw material liquid is adjusted to a predetermined electrical conductivity.
  • FIG. 5 is a schematic view showing a desalting process flow of an ultrafiltration device which is an example of a desalting device used for production of vanadium dioxide-containing particles according to the present invention.
  • the ultrafiltration device (50) shown in FIG. 5 includes an adjustment kettle (51) for storing the slurry raw material liquid (52), and a replenishment ion exchange water stock kettle (57) for replenishment ion exchange water (58). ), A replenishment ion exchange water supply line (59) for adding replenishment ion exchange water (58) to the adjustment pot (51), and a circulation line (53) for circulating the adjustment pot (51) by a circulation pump (54). ), An ultrafiltration unit (55) as a desalting means in the path of the circulation line (53), and an electric conductivity meter (60) in the adjustment pot (51).
  • Step (I) The slurry raw material liquid (52) containing the vanadium-containing compound, the compound that reacts with the vanadium-containing compound and the ion-exchanged water prepared by the method described above is stored in the adjustment kettle (51), and the circulation pump (54) is provided. While being used and circulated, the ultrafiltration section (55) discharges moisture containing salts in the slurry raw material liquid from the discharge port (56) at a discharge amount V1, and concentrates the slurry raw material liquid to a predetermined concentration. .
  • the slurry raw material liquid (52) concentrated in the ultrafiltration unit (55) is supplied from the supplementary ion exchange water stock kettle (57) via the supplementary ion exchange water supply line (59).
  • Addition-supplemented ion-exchange water (58) having the same capacity as the discharge amount V1 at the filtration unit (55) is added at the addition amount V2, and sufficiently stirred and mixed to obtain the first desalted slurry raw material liquid (52).
  • the electrical conductivity ( ⁇ S / m) of the primary desalted slurry raw material liquid (52) is measured by the electrical conductivity meter (60).
  • Step (III) Next, in the same manner as in the above step (I), the constituent liquid (ion-exchanged water + salts) in the slurry raw material liquid (52) is discharged by the ultrafiltration part (55) while being circulated by the circulation pump (54). Discharge (56) out of the system by the amount V1.
  • Examples of the ultrafiltration method used in the above desalting treatment step include No. of Research Disclosure. 10208 (1972), no. 13122 (1975) and no. Reference can be made to the described methods such as 16351 (1977).
  • the organic membranes that make up the membrane materials include flat plate types, spiral types, cylindrical types, hollow fiber types, and hollow fiber types that are already incorporated as modules.
  • ceramic films such as NGK Co., Ltd. and Noritake Company Limited are preferred as the film having solvent resistance.
  • a Vivaflow 50 (effective filtration area 50 cm 2 , molecular weight cut off 5000) manufactured by Sartorius steady is used as a filtration membrane, and ultrafiltration is performed at a flow rate of 300 mL / min, a hydraulic pressure of 100 kPa, and room temperature.
  • Examples thereof include an ultrafiltration apparatus (Pericon 2 cassette manufactured by Merck Millipore Corporation) having a filtration membrane made of polyethersulfone and having a molecular weight cut off of 300,000.
  • the slurry raw material liquid subjected to the desalting treatment has an average primary particle size of 15 to 15 by hydrothermal synthesis as shown in the third step of the flow chart of FIG.
  • Vanadium dioxide-containing particles having an average crystallite size in the range of 15 to 40 nm in the range of 40 nm are produced.
  • FIG. 6 is a schematic diagram showing a preferred production flow under production conditions 3 (embodiment 3) applied to the method for producing vanadium dioxide-containing particles of the present invention.
  • the raw material liquid container 1 (5) for storing the desalted slurry raw material liquid contains 1) a vanadium-containing compound, 2) a compound that reacts with the vanadium-containing compound, for example, ion-exchanged water. Alkali dissolved at a predetermined concentration and 3) ion-exchanged water are added, ion-exchanged water is added as water to the other raw material liquid container 2 (2), and this ion-exchanged water is predetermined by a heating medium (13).
  • production conditions applied to production condition 3 for example, the configuration of a flow reactor having a hydrothermal reaction section (FIG. 2), hydrothermal reaction conditions, preparation of slurry raw material liquid, slurry raw material liquid Constituent materials (vanadium-containing compounds, alkalis, various additives, etc.) are appropriately selected according to the above-described production conditions 1 (embodiment 1) or production conditions 2 (embodiment 2). And can be applied.
  • Embodiment 4 using a flow reactor having a hydrothermal reaction section, a slurry raw material liquid containing at least a vanadium-containing compound and water, a compound that reacts with the vanadium-containing compound, and a supercritical or subcritical state
  • the slurry raw material liquid is dispersed before the step of producing the vanadium dioxide-containing particles.
  • a step of treating, and adjusting a particle size distribution width of the vanadium dioxide-containing particles to 80 nm or less.
  • production condition 4 is applied, and the slurry raw material liquid is subjected to a dispersion treatment in advance before carrying out hydrothermal synthesis using a flow reactor, and the vanadium-containing compound in the slurry raw material liquid
  • the particle size distribution width of the vanadium dioxide-containing particles after hydrothermal synthesis can be narrowed and the thermochromic properties can be improved.
  • the production condition 4 according to the present invention is characterized in that the slurry raw material liquid is subjected to a dispersion treatment before hydrothermal reaction of the slurry raw material liquid.
  • the method for dispersing the slurry raw material liquid is not particularly limited, but for example, dispersion by adding a dispersing agent such as high-pressure dispersion, media dispersion, ultrasonic dispersion, or surfactant (hereinafter also referred to as chemical dispersion).
  • a dispersing agent such as high-pressure dispersion, media dispersion, ultrasonic dispersion, or surfactant (hereinafter also referred to as chemical dispersion).
  • high-pressure dispersion enables dispersion without damaging the slurry raw material (without changing the shape).
  • any one method may be employ
  • High-pressure dispersion means that the slurry raw material pressurized at high pressure is sheared by a high flow rate, abrupt pressure drop (cavitation), and a high-velocity particle is crushed by the impact force caused by collision of particles in a fine orifice.
  • the dispersion method using a high-pressure homogenizer is performed, and examples of commercially available devices include Nanohausa (manufactured by Yoshida Kikai Kogyo Co., Ltd.), Nanomizer (manufactured by Nanomizer Co., Ltd.), and Microfluidizer (manufactured by Microfluidics).
  • beads as a medium are filled in a container, and a slurry raw material liquid composed of at least vanadium-containing compound particles and a medium (for example, water) is poured into the agitated beads.
  • a slurry raw material liquid composed of at least vanadium-containing compound particles and a medium (for example, water)
  • the vanadium-containing compound particles are pulverized (micronized) and the aggregates are peptized by stirring together with the beads.
  • centrifugation for separating the slurry and the beads.
  • beads used for media dispersion include ceramic beads, glass beads, steel beads, silicon nitride beads, zirconia beads, and alumina beads.
  • paint shaker made by RED DEVIL
  • star mill ZRS made by Ashizawa Finetech Co., Ltd.
  • ultra apex mill made by Hiroshima Metal & Machinery Co., Ltd.
  • MSC-MILL Natural Coke Industry Co., Ltd.
  • Ultrasonic dispersion is a method of dispersing a slurry raw material liquid within an oscillation frequency range of 20 to 200 kHz.
  • An apparatus used for ultrasonic dispersion includes an ultrasonic disperser (manufactured by SMT).
  • Chemical dispersion is a method of dispersing a slurry raw material by adding a dispersant such as a surfactant into the slurry raw material liquid.
  • the dispersant used for chemical dispersion is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include glycine, threonine, sarcosine, alanine, and polyvinylpyrrolidone (PVP).
  • the addition amount of the dispersant is preferably in the range of 5 to 20% by mass with respect to the vanadium-containing compound (100% by mass).
  • the dispersed particle size after dispersion treatment of the vanadium-containing compound in the slurry raw material liquid it is preferable to adjust the dispersed particle size after dispersion treatment of the vanadium-containing compound in the slurry raw material liquid to 300 nm or less. If the dispersed particle size is 300 nm or less, the haze and ⁇ TSER of the optical film can be improved. ⁇ TSER is the difference in thermal insulation (TSER) between a low temperature environment and a high temperature environment. It is considered that the dispersed particle size after the dispersion treatment determines the dispersed particle size of the vanadium dioxide-containing particles after hydrothermal synthesis. If the dispersed particle size of the vanadium dioxide-containing particles is small, the specific surface area increases and the vanadium dioxide-containing particles are contained. We believe that the light absorption capacity of the particles will increase, leading to an improvement in ⁇ TSER.
  • the dispersed particle size is obtained by calculating the average particle size (Z average) by a dynamic light scattering (Dynamic Light Scattering: DLS) method using a dynamic light scattering analyzer (Zetasizer Nano S manufactured by Malvern). This value is determined as the dispersed particle size.
  • DLS Dynamic Light Scattering: DLS
  • Zetasizer Nano S manufactured by Malvern a dynamic light scattering analyzer
  • adjusting the particle size distribution width to 80 nm or less means adjusting the particle size of the vanadium dioxide-containing particles to be measured to 80 nm or less.
  • the particle size distribution width of the vanadium dioxide-containing particles was evaluated with a scanning electron microscope (FE-SEM) (manufactured by Hitachi, Hitachi S-4300 type), and an SEM photograph (1250 nm ⁇ 850 nm) was used.
  • the particle size is calculated and created.
  • the particle diameter means an area equivalent circle diameter.
  • the SEM photograph the area of each particle is measured, and the diameter of a circle having the same area is defined as the particle diameter.
  • 30 particles having the most universal size and shape are selected, and the average particle size of the 30 particles is calculated.
  • the particle size range is divided every 5 nm, a histogram is created, and this distribution is defined as the particle size distribution width.
  • the vanadium dioxide-containing particles produced by the production conditions 1 to 4 according to the present invention are characterized by having a small particle size and a narrow particle size distribution.
  • the average particle diameter (D) of the vanadium dioxide-containing particles is not particularly limited, but within the range of 1 to 40 nm. It is preferably within the range of 1 to 30 nm, more preferably within the range of 1 to 25 nm, particularly preferably within the range of 1 to 15 nm, and within the range of 1 to 10 nm. Most preferably. With vanadium dioxide-containing particles having such a particle size, haze can be satisfactorily lowered and thermochromic properties can be effectively expressed.
  • grains can be measured by the particle size measuring method based on electron microscope observation or a dynamic light scattering method.
  • the fluid is analyzed by the dynamic light scattering (Dynamic Light Scattering, DLS) method using a dynamic light scattering analyzer (DLS-8000, manufactured by Otsuka Electronics Co., Ltd.). Measure the mechanical diameter.
  • DLS Dynamic Light Scattering
  • DLS-8000 dynamic light scattering analyzer
  • the average particle diameter (D) (nm) of the vanadium dioxide-containing particles can be measured by the following method.
  • the dispersion containing vanadium dioxide-containing particles and water was mixed with water so that the concentration of vanadium dioxide-containing particles was 0.01% by mass with respect to the total mass of the dispersion, respectively, and dispersed with ultrasound for 15 minutes. Prepare a sample for measurement.
  • the hydrodynamic diameter (nm) is measured by a dynamic light scattering (Dynamic Light Scattering, DLS) method using a dynamic light scattering analyzer (DLS-8000, manufactured by Otsuka Electronics Co., Ltd.). Based on this, the average particle size of the particle size distribution by cumulant analysis is obtained, and this value is taken as the average particle size (D) (nm).
  • DLS Dynamic Light Scattering
  • the particle size distribution of the vanadium dioxide-containing particles is not particularly limited, but when the polydispersity index (PDI) is used as an index, the polydispersity index (PDI) is preferably less than 0.30. More preferably within the range of 0.01 to 0.25, even more preferably within the range of 0.01 to 0.15, particularly preferably within the range of 0.01 to 0.10, Most preferably, it is within the range of 0.01 to 0.08.
  • the vanadium dioxide-containing particles having a particle size distribution exhibiting such a polydispersity index (PDI) effectively improve the thermochromic properties of the vanadium dioxide-containing particles and the transparency of the optical film to which the vanadium dioxide-containing particles are applied. it can.
  • the value measured by the following method is employ
  • the polydispersity index (PDI) is a numerical value calculated on the assumption that the particle size distribution is a normal distribution in the cumulant analysis measured by the dynamic light scattering method (DLS method) in the same manner as the measurement of the average particle size (D). did.
  • the average primary particle size of the produced vanadium dioxide-containing particles is 15 to
  • the average crystallite diameter is in the range of 40 to 40 nm, and the average crystallite diameter is in the range of 15 to 40 nm.
  • the average primary particle size of the vanadium dioxide-containing particles is characterized by being in the range of 15 to 40 nm, preferably in the range of 15 to 30 nm, and more preferably in the range of 15 to 25 nm. .
  • the particle diameter of the vanadium dioxide-containing particles can be measured by an electron microscope observation or a particle diameter measurement method based on a dynamic light scattering method.
  • the average primary particle diameter (D) (nm) of the vanadium dioxide-containing particles can also be measured by the following method.
  • a dispersion containing vanadium dioxide-containing particles and water is dried and solidified in an oven at 120 ° C. to form a powder, and a particle sample for measurement is prepared.
  • an SEM photograph is taken with a scanning electron microscope (manufactured by Hitachi, Hitachi S-5000 type).
  • the particle diameter is calculated using an SEM photograph (1100 nm ⁇ 950 nm).
  • the particle diameter means an area equivalent circle diameter.
  • the SEM photograph the area of each particle was measured, and the diameter of a circle having the same area was taken as the particle diameter of the particle.
  • 30 particles having the most universal size and shape were selected, the average primary particle size of 30 particles was calculated, and the average value was defined as the average primary particle size (D) (nm).
  • the average crystallite size of the vanadium dioxide-containing particles is characterized by being in the range of 15 to 40 nm, preferably in the range of 15 to 30 nm, and preferably in the range of 15 to 25 nm. Further preferred.
  • crystallite refers to the largest region of microcrystals present as a complete single crystal in a polycrystalline particle.
  • FIG. 7 is a schematic diagram showing an example of the particle structure of vanadium dioxide-containing particles according to the present invention.
  • the vanadium dioxide-containing particles (P) according to the present invention are formed of a plurality of crystallites (CL).
  • the average crystallite diameter of the vanadium oxide-containing particles is obtained.
  • D shown in FIG. 7 is an average primary particle diameter of vanadium dioxide containing particle
  • the obtained average crystallite diameter (A) represents the size of crystals growing in the same direction in the crystal grains. That the average crystallite diameter (A) is small means that crystallites (CL) growing in the same specific direction in the crystal grains are small.
  • crystallites (CL) grow, so that crystal grains having a crystallite diameter (A) larger than the particle diameter (D) are formed.
  • the average crystallite diameter (A) according to the present invention can be calculated by the XRD (X-ray diffraction) measurement using the Scherrer formula shown in the following formula (2).
  • Formula (2) A K ⁇ / ⁇ cos ⁇
  • K is the Scherrer constant and ⁇ is the X-ray wavelength.
  • ⁇ is the half width of the diffraction line.
  • ⁇ is the Bragg angle with respect to the diffraction line.
  • thermochromic property is obtained by preparing a dispersion containing such particles and applying the dispersion. As a result, the influence of haze can be reduced, and as a result, a highly transparent optical film containing vanadium dioxide-containing particles can be obtained.
  • reaction liquid after the hydrothermal reaction process or the cooling liquid after the cooling process may be used as the dispersion liquid as it is, or the reaction liquid or the cooling liquid (reaction liquid) after the hydrothermal reaction process. It may be diluted by adding water or alcohol, and the dispersion medium of the reaction liquid or cooling liquid (reaction liquid) after the hydrothermal reaction step may be replaced with water or alcohol to prepare a dispersion liquid.
  • the method for dispersing the vanadium dioxide-containing particles is not particularly limited, and a known dispersing device such as an ultrasonic dispersing machine may be used.
  • the dispersion medium of the dispersion may be composed only of water.
  • an organic solvent of about 0.1 to 10% by mass (in the dispersion), for example, methanol, ethanol, isopropanol, Alcohols such as butanol and ketones such as acetone may also be included.
  • a phosphate buffer, a phthalate buffer, etc. can also be used.
  • the dispersion may be adjusted to a desired pH using an organic or inorganic acid or alkali such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phthalic acid, ammonium hydroxide, or ammonia.
  • an organic or inorganic acid or alkali such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phthalic acid, ammonium hydroxide, or ammonia.
  • the pH of the dispersion is preferably 4-7.
  • the concentration of the vanadium dioxide-containing particles in the dispersion is preferably in the range of 0.01 to 40% by mass with respect to the total mass of the dispersion, 0.5 to 40
  • the content is more preferably in the range of mass%, more preferably in the range of 1 to 30 mass%.
  • the vanadium dioxide-containing particles according to the present invention can be preferably used for an optical film.
  • the optical film here has a transparent base material and an optical functional layer formed on the transparent base material, and the optical functional layer contains a resin and vanadium dioxide (VO 2 ) -containing particles according to the present invention. It is the film which expresses the thermochromic property which consists of a structure to do.
  • the haze is preferably 4% or less, more preferably 2% or less.
  • the haze of the optical film can be measured at room temperature (25 ° C.) using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the ⁇ TSER of the optical film is in the range of 5 to 20%, preferably in the range of 10 to 20%.
  • ⁇ TSER of the optical film is specifically determined by using a spectrophotometer (using an integrating sphere, manufactured by Hitachi, Ltd., U-4000 type) in the region of 300 to 2500 nm and transmitting light every 2 nm. Measure the rate and light reflectance. In that case, it adjusts so that the temperature of an optical film may become low temperature (10 degreeC) and high temperature (70 degreeC).
  • the transparent base material applicable to the optical film is not particularly limited as long as it is transparent, and examples thereof include glass, quartz, and a transparent resin film. However, it is possible to provide flexibility and suitability for production (roll-to-roll suitability). From the viewpoint, 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's it.
  • the thickness of the transparent substrate is preferably in the range of 30 to 200 ⁇ m, more preferably in the range of 30 to 100 ⁇ m, and still more preferably in the range of 35 to 70 ⁇ m. If the thickness of the transparent substrate is 30 ⁇ m or more, wrinkles and the like are less likely to occur during handling, and if the thickness is 200 ⁇ m or less, when producing laminated glass, to the curved glass surface when bonding to the glass substrate The follow-up performance is improved.
  • the transparent base material has a thermal shrinkage within a range of 0.1 to 3.0% at a temperature of 150 ° C. from the viewpoint of preventing generation of wrinkles of the optical film and cracking of the infrared reflecting layer. Is more preferable, being in the range of 1.5 to 3.0%, more preferably 1.9 to 2.7%.
  • the transparent substrate applicable to the optical film is not particularly limited as long as it is transparent, but various transparent resin films are preferably used.
  • a polyolefin film for example, Polyethylene film, polypropylene film, etc.
  • polyester film eg, polyethylene terephthalate film, polyethylene naphthalate film, etc.
  • polyvinyl chloride film eg, polyethylene terephthalate film, polyethylene naphthalate film, etc.
  • triacetyl cellulose film preferably polyester film, triacetyl cellulose film. More preferably, it is a polyester film.
  • the polyester film (hereinafter simply referred to as “polyester”) is not particularly limited, but is preferably a polyester having a film-forming property having a dicarboxylic acid component and a diol component as main components.
  • the main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid.
  • diol component examples include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.
  • polyesters having these as main components from the viewpoints of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred.
  • dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1
  • polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred.
  • polyethylene terephthalate, polyethylene naphthalate, polyesters containing these as main constituents, copolymer polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and two or more of these polyesters A polyester having a mixture as a main constituent is preferred.
  • the transparent resin film is particularly preferably a biaxially oriented polyester film, but a uniaxially stretched polyester film that is unstretched or stretched at least in one direction can also be used.
  • a stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression.
  • a stretched film is more preferable.
  • particles when a transparent resin film is used as the transparent substrate, particles may be contained within a range that does not impair transparency in order to facilitate handling.
  • particles applicable to the transparent resin film include inorganic particles such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide. And organic particles such as crosslinked polymer particles and calcium oxalate.
  • the method of adding particles include a method of incorporating particles in a resin (for example, polyester) used as a raw material for forming a film, a method of directly adding to an extruder, and the like.
  • additives may be added to the transparent resin film as necessary.
  • additives include stabilizers, lubricants, cross-linking agents, anti-blocking agents, antioxidants, dyes, pigments, and ultraviolet absorbers.
  • a transparent resin film that is a transparent substrate can be produced by a conventionally known general method.
  • a dope is prepared by mixing a resin as a material with a solvent, and the dope is cast on a continuous support to form a film, and then partially dried on an endless support that rotates continuously. Later, it is peeled off from the endless support, then sufficiently dried, and optionally subjected to a stretching process during the drying or after drying to produce an unstretched or stretched transparent resin film.
  • a dope is prepared by mixing a resin as a material with a solvent, and the dope is cast on a continuous support to form a film, and then partially dried on an endless support that rotates continuously. Later, it is peeled off from the endless support, then sufficiently dried, and optionally subjected to a stretching process during the drying or after drying to produce an unstretched or stretched transparent resin film.
  • a melt flow is produced by melting a resin as a material with an extruder, extruding with an annular die or a T-die and quenching, thereby producing an unstretched transparent resin film that is substantially amorphous and not oriented. It can be produced by the elongation method.
  • the transparent resin film can be transported in the direction of the transparent resin film (vertical axis direction) by a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. , MD direction) or a transparent resin film can be produced by stretching in a horizontal axis direction (width direction, TD direction) perpendicular to the transport direction of the transparent resin film.
  • the stretching ratio in this case can be appropriately selected according to the resin used as the raw material of the transparent resin film, but it is preferable to stretch the film within the range of 2 to 10 times in the vertical axis direction and the horizontal axis direction.
  • the transparent resin film may be subjected to relaxation treatment or offline heat treatment in terms of dimensional stability.
  • the relaxation treatment is preferably performed, for example, in a process from heat setting in a stretch film forming process of a polyester film to a winding process after exiting the tenter.
  • the relaxation treatment is preferably carried out at a treatment temperature in the range of 80 to 200 ° C., and a more preferred treatment temperature is in the range of 100 to 180 ° C.
  • the relaxation rate is preferably in the range of 0.1 to 10% in both the transport direction and the horizontal axis direction, and more preferably, the relaxation rate is in the range of 2 to 6%.
  • the relaxed substrate is subjected to off-line heat treatment to improve heat resistance and to improve dimensional stability.
  • the transparent resin film is preferably coated with the undercoat layer coating solution in-line on one or both sides during the film forming process.
  • the resins used for the undercoat layer coating solution useful for transparent resin films include polyester resin, (meth) acryl-modified polyester resin, polyurethane resin, acrylic resin, vinyl resin, vinylidene chloride resin, polyethyleneimine vinylidene resin, polyethylene Examples thereof include imine resin, polyvinyl alcohol resin, modified polyvinyl alcohol resin, and gelatin, and any of them can be preferably used.
  • a conventionally well-known additive can also be added to these undercoat layers.
  • the undercoat layer can be coated by a known method such as roll coating, gravure coating, knife coating, dip coating or spray coating.
  • the coating amount of the undercoat layer is preferably about 0.01 to 2 g / m 2 (dry state).
  • An optical functional layer containing the resin and the vanadium dioxide-containing particles according to the present invention is provided on the transparent substrate of the optical film.
  • the resin applicable to the formation of the optical functional layer is not particularly limited, and the same resins that are generally used for the optical functional layer of the optical film can be used, preferably a water-soluble polymer is used. it can.
  • the “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, hydrophilic polymer typified by gelatin described in JP-A-2006-343391), starch, guar gum, alginate, methylcellulose, and ethylcellulose.
  • 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 of the optical functional layer from the viewpoint of obtaining a desired thermochromic property. % Is more preferable.
  • additives can be used in the optical functional layer as long as the effects are not impaired.
  • a list of various applicable additives is listed below.
  • surfactants such as cation or nonion, JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-242 209266, etc.
  • optical brighteners sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate and other pH adjusters
  • antifoaming agents Lubricants such as diethylene glycol, antiseptics, antifungal agents, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, viscosity reducing agents, lubricants, infrared absorbers
  • additives such as dyes and pigments.
  • the method for producing the optical film (the method for forming the optical functional layer) is not particularly limited, and can be applied in the same manner or appropriately modified except that the vanadium dioxide-containing particles according to the present invention are used. Specifically, a method in which a coating solution containing vanadium dioxide-containing particles is prepared, and the coating solution is coated on a transparent substrate by a wet coating method and dried to form an optical functional layer is preferable.
  • the wet coating method is not particularly limited, and 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 US Pat. No. 2,761,419, US Examples thereof include a slide hopper coating method and an extrusion coating method described in Japanese Patent No. 27671791.
  • Example 1 and Example 2 that demonstrate the specific effects of Production Condition 1 (Embodiment 1) according to the present invention are shown below.
  • Example 1 Preparation of vanadium dioxide-containing particles >> [Preparation of vanadium dioxide-containing particles 1: comparative example] 19.0 g of vanadium oxide sulfate (IV) (VOSO 4 ) was dissolved in ion-exchanged water (dissolved oxygen amount: 8.1 mg / L) to 300 mL, and while stirring this solution, 3.0 mol / L as an alkali was added. Reaction solution 1 was prepared by adding 68 g of NH 3 aqueous solution and adjusting pH to 8.0. This reaction liquid 1 was put into an autoclave having an internal volume of 500 mL and subjected to a hydrothermal reaction treatment at 250 ° C. and 3.98 MPa for 8 hours to form vanadium dioxide (VO 2 ) -containing particles 1. Subsequently, the reaction liquid was cooled and the dispersion liquid containing the vanadium dioxide containing particle
  • V 2 vanadium oxide sulfate
  • a raw material liquid container 1 (5) shown in FIG. 2 19.0 g of vanadium oxide (IV) sulfate (VOSO 4 ) is dissolved in ion-exchanged water (dissolved oxygen amount: 8.1 mg / L) to make 300 mL. While stirring the liquid, 68 mL of 3.0 mol / L NH 3 aqueous solution was added as an alkali to prepare a raw material liquid 1 having a pH of 8.0. On the other hand, ion exchange water (dissolved oxygen amount: 8.1 mg / L) was stored as the raw material liquid 2 in the raw material liquid container 2 (2) shown in FIG.
  • ion exchange water dissolved oxygen amount: 8.1 mg / L
  • the raw material liquid 1 containing vanadium oxide sulfate (IV) and alkali is fed from the raw material liquid container 1 (5) through the flow path (6) by a pump (7), and heated at 25 ° C. with a heating medium (15). Pressurization was performed so that the condition was 30 MPa.
  • the ion exchange water as the raw material liquid 2 is fed from the raw material liquid container 2 (2) through the flow path (3) by the pump (4), and is heated by the heating medium (13) at 440 ° C. and 30 MPa. Was heated and pressurized to obtain supercritical water.
  • the raw material liquid 1 containing vanadium oxide (IV) oxide and alkali and the raw material liquid 2 which is supercritical water at the junction (MP) shown in FIG. The mixture was mixed under the conditions of 4 to form a reaction liquid 2, which was fed to the hydrothermal reaction section (16) which is a hydrothermal reaction section. In the hydrothermal reaction part, it sent to the heating part piping (17) arrange
  • the treatment time (passage time) was 2 seconds under the conditions of 400 ° C. and 30 MPa, and vanadium dioxide (VO 2 ) -containing particles were formed.
  • the reaction liquid 2 was cooled in the cooling part (8), and the dispersion liquid containing the vanadium dioxide containing particle
  • the amount of dissolved oxygen that was deaerated using a membrane deaerator having a hollow fiber membrane instead of the ion exchange water used in the preparation of the raw material liquid 1 and the raw material liquid 2 A dispersion containing vanadium dioxide-containing particles 3 and water was prepared in the same manner except that 4.0 mg / L of degassed water was used.
  • vanadium dioxide-containing particles 7 to 9 In the preparation of the vanadium dioxide-containing particles 3 to 5, vanadium dioxide was similarly obtained except that hydrazine was added to the raw material liquid 1 and the raw material liquid 2 under the condition of 0.15% by mass as a reducing compound. Each dispersion containing the contained particles 7 to 9 was prepared.
  • vanadium dioxide-containing particles 13 to 15 In the preparation of the vanadium dioxide-containing particles 3 to 5, vanadium dioxide was similarly prepared except that formic acid was added as a reducing compound to raw material liquid 1 and raw material liquid 2 under the condition of 0.15% by mass. Each dispersion containing the contained particles 13 to 15 was prepared.
  • a raw material liquid container 1 (5) shown in FIG. 2 19.0 g of vanadium oxide (IV) sulfate (VOSO 4 ) is dissolved in ion-exchanged water (dissolved oxygen amount: 8.1 mg / L) to make 300 mL. was used as the raw material liquid 1.
  • VOSO 4 vanadium oxide
  • ion-exchanged water dissolved oxygen amount: 8.1 mg / L
  • ion exchange water (dissolved oxygen amount: 8.1 mg / L) containing 3.0 mol / L NH 3 as an alkali was stored as the raw material liquid 2. .
  • the raw material liquid 1 containing vanadium oxide sulfate (IV) is fed from the raw material liquid container 1 (5) through the flow path (6) by a pump (7), and heated by a heating medium (15) at 25 ° C. and 30 MPa. Pressurization was performed to satisfy the conditions.
  • the raw material liquid 2 containing sodium hydroxide as the raw material liquid 2 is fed from the raw material liquid container 2 (2) through the flow path (3) by the pump (4), and is heated to 440 ° C. by the heating medium (13).
  • supercritical water was obtained by heating and pressing under the condition of 30 MPa.
  • the raw material liquid 1 containing vanadium oxide (IV) oxide at the junction (MP) shown in FIG. 2 and the raw material liquid 2 that is supercritical water containing alkali are subjected to the conditions that the pH of the reaction liquid becomes 8.0.
  • the mixture was mixed to form a reaction liquid 35, which was sent to the hydrothermal reaction section (16), which is a hydrothermal reaction section.
  • the hydrothermal reaction part it sent to the heating part piping (17) arrange
  • the treatment time (passage time) was 2 seconds under the conditions of 400 ° C. and 30 MPa, and vanadium dioxide (VO 2 ) -containing particles were formed.
  • the reaction liquid 16 was cooled in the cooling part (8), and the dispersion liquid containing the vanadium dioxide containing particle
  • the amount of dissolved oxygen subjected to a deaeration process using a membrane deaerator having a hollow fiber membrane instead of the ion exchange water used for the preparation of the raw material liquid 1 and the raw material liquid 2 A dispersion containing vanadium dioxide-containing particles 17 and water was prepared in the same manner except that 4.0 mg / L of degassed water was used.
  • vanadium dioxide-containing particles 21-22 In the preparation of the vanadium dioxide-containing particles 17 to 18, vanadium dioxide was similarly obtained except that hydrazine was added as a reducing compound to the raw material liquid 1 and the raw material liquid 2 under the condition of 0.15% by mass. Each dispersion containing the contained particles 21 to 22 was prepared.
  • vanadium dioxide-containing particles 25-26 In the preparation of the vanadium dioxide-containing particles 17 to 18, vanadium dioxide was similarly prepared except that formic acid was added to the raw material liquid 1 and the raw material liquid 2 under the condition of 0.15% by mass as a reducing compound. Each dispersion containing the contained particles 25 to 26 was prepared.
  • the hydrodynamic diameter (nm) was measured by a dynamic light scattering (DLS) method using a dynamic light scattering analyzer (DLS-8000, manufactured by Otsuka Electronics Co., Ltd.). And based on this, the average particle diameter of the particle size distribution by cumulant analysis was calculated
  • D average particle diameter
  • the polydispersity index (PDI) is calculated on the assumption that the particle size distribution is a normal distribution in the cumulant analysis measured by the dynamic light scattering method (DLS method) in the same manner as the measurement of the average particle size (D). It was set as a numerical value.
  • thermochromic properties evaluation of thermochromic properties (TC1) immediately after preparation)
  • the dispersion liquid containing each vanadium dioxide-containing particle prepared above was filtered at a flow rate of 300 mL / min and a hydraulic pressure of 0.1 MPa using Vivaflow 50 (effective filtration area 50 cm 2 , fractional molecular weight 5000) manufactured by Sartorius steady. Concentration adjustment is performed, and vanadium dioxide-containing particles are added to polyvinyl alcohol so that the ratio of vanadium dioxide-containing particles to the total mass of polyvinyl alcohol and vanadium dioxide-containing particles is 10% by mass to prepare a coating solution. did.
  • the film for measurement 1 is prepared by coating and drying on a 50 ⁇ m thick polyethylene terephthalate (PET) substrate manufactured by Teijin DuPont Films, Ltd., and forming a layer containing vanadium dioxide containing particles having a dry film thickness of 3 ⁇ m. did.
  • PET polyethylene terephthalate
  • thermochromic TC1 (% Specifically, the transmittance at a wavelength of 2000 nm (T 25 ° C. ) and the environment at 85 ° C. and 50% RH) was evaluated in an environment of 25 ° C. and 50% RH.
  • the transmittance at a wavelength of 2000 nm (T 85 ° C. ) was measured to determine the transmittance difference 1 immediately after preparation (T 85 ° C.- T 25 ° C. ), and this was used as a measure of thermochromic properties (TC 1) immediately after preparation. Evaluation was made according to criteria. The measurement was performed by attaching a temperature control unit (manufactured by JASCO Corporation) to a spectrophotometer V-670 (manufactured by JASCO Corporation).
  • Transmittance difference 1 (T 85 ° C.- T 25 ° C. ) is 70% or more 4: Transmittance difference 1 (T 85 ° C.- T 25 ° C. ) is 50% or more and less than 70% 3: Transmittance difference 1 (T 85 ° C. ⁇ T 25 ° C. ) is 40% or more and less than 50% 2: Transmittance difference 1 (T 85 ° C. ⁇ T 25 ° C. ) is 25% or more and less than 40% 1: Transmittance difference 1 (T 85 ° C. ⁇ T 25 ° C.
  • the dispersion containing the vanadium dioxide-containing particles subjected to the forced deterioration treatment was flowed at 300 mL / min with a flow rate of 0 using a Vivaflow 50 (effective filtration area 50 cm 2 , molecular weight cut-off 5000) manufactured by Sartorius steady.
  • the concentration is adjusted by filtration at 1 MPa so that the vanadium dioxide-containing particles in polyvinyl alcohol have a ratio of vanadium dioxide-containing particles to 10% by mass with respect to the total mass of polyvinyl alcohol and vanadium dioxide-containing particles.
  • the film for measurement 2 in which a layer containing vanadium dioxide containing particles having a dry film thickness of 3 ⁇ m was formed by applying and drying onto a 50 ⁇ m-thick polyethylene terephthalate (PET) substrate manufactured by Teijin-Dupont Film Co., Ltd. did.
  • PET polyethylene terephthalate
  • ⁇ Measurement of transmittance decrease width ⁇ T> The reduction width ⁇ T (%) of the transmittance difference 2 (T 85 ° C.- T 25 ° C. ) after the forced deterioration treatment with respect to the transmittance difference 1 (T 85 ° C.- T 25 ° C. ) immediately after the preparation as measured above is obtained by the following equation. This was evaluated according to the following criteria as a measure of durability.
  • Reduced transmittance ⁇ T (%) [(transmittance difference 1 immediately after preparation (T 85 ° C. ⁇ T 25 ° C. ) ⁇ Transmittance difference 2 after forced deterioration treatment (T 85 ° C. ⁇ T 25 ° C. )) / Preparation Transmittance difference 1 immediately after (T 85 ° C.- T 25 ° C.
  • the transmittance decrease width ⁇ T is less than 2.0% 4: The transmittance decrease width ⁇ T is 2.0% or more and less than 5.0% 3: The transmittance decrease width ⁇ T is 5.0% or more and less than 10.0% 2: The transmittance decrease width ⁇ T is 10.0% or more and less than 20.0% 1: The transmittance decrease width ⁇ T is 20.0% The results obtained as described above are shown in Table II.
  • thermochromic property (TC1) and the rate of decrease in thermochromic property ( ⁇ T) after the forced deterioration treatment are low.
  • the vanadium dioxide (VO 2 ) -containing particles prepared under the production condition 1 (embodiment 1) according to the present invention have a smaller average particle diameter (D) than that of the comparative example and have a polydispersity index (PDI). It was proved that the particle size distribution was small and the thermochromic property was excellent.
  • Example 2 Preparation of vanadium dioxide-containing particles >> [Preparation of vanadium dioxide-containing particles 31: comparative example] Ammonium vanadate (V) (NH 4 VO 3 , Wako Pure Chemical Industries, Ltd., special grade) 7.1 g was dissolved in ion exchange water (dissolved oxygen amount: 8.1 mg / L) at 325.0 g at 60 ° C. While stirring this solution, 16.9 g of 0.95 mol / L hydrazine hydrate (N 2 H 4 ⁇ H 2 O, manufactured by Wako Pure Chemical Industries, Ltd., special grade) was slowly added dropwise to pH 9.5. Added until.
  • V Ammonium vanadate
  • ion exchange water dissolved oxygen amount: 8.1 mg / L
  • This reaction liquid 51 was put into an autoclave having an internal volume of 500 mL, and subjected to a hydrothermal reaction treatment at 250 ° C. and 3.98 MPa for 12 hours to form vanadium dioxide (VO 2 ) -containing particles 31. Subsequently, the reaction liquid was cooled and the dispersion liquid containing the vanadium dioxide containing particle
  • VO 2 vanadium dioxide
  • a raw material liquid container 1 (5) shown in FIG. 2 7.1 g of ammonium vanadate (V) (NH 4 VO 3 , Wako Pure Chemical Industries, Ltd., special grade) was added to ion-exchanged water (dissolved oxygen amount) at 60 ° C. : 8.1 mg / L) dissolved in 325.0 g, and stirring this solution, 0.95 mol / L hydrazine hydrate (N 2 H 4 .H 2 O, Wako Pure Chemical Industries, Ltd. as compound (B))
  • a raw material solution 1 was prepared by slowly dropping 16.9 g of an aqueous solution (manufactured by Co., Ltd.) and adding it until pH 9.5 was reached.
  • ion exchange water was stored as the raw material liquid 2 in the raw material liquid container 2 (2) shown in FIG.
  • the raw material liquid 1 containing ammonium vanadate (V) and hydrazine hydrate is fed from the raw material liquid container 1 (5) through the flow path (6) by the pump (7), and heated by the heating medium (15). Heating and pressurization were performed at 30 ° C. so as to satisfy the condition of 30 MPa.
  • ion exchange water (dissolved oxygen amount: 8.1 mg / L) as the raw material liquid 2 is sent from the raw material liquid container 2 (2) through the flow path (3) by the pump (4), and the heating medium ( 13), supercritical water was obtained by heating and pressing at 440 ° C. and 30 MPa.
  • the raw material liquid 1 containing ammonium vanadate (V) and hydrazine hydrate and the raw material liquid 2 which is supercritical water at the confluence (MP) shown in FIG. It mixed on the conditions used as 2 1: 4, the reaction liquid 32 was formed, and it liquid-fed to the hydrothermal reaction part (16) which is a hydrothermal reaction part. In the hydrothermal reaction part, it sent to the heating part piping (17) arrange
  • the treatment time (passage time) was 2 seconds under the conditions of 400 ° C. and 30 MPa, and the vanadium dioxide (VO 2 ) -containing particles 32 were formed.
  • the reaction liquid 2 was cooled in the cooling part (8), and the dispersion liquid containing the vanadium dioxide containing particle
  • Embodiment 1A a dispersion containing vanadium dioxide-containing particles 33 was prepared according to the following method using the flow reactor having the hydrothermal reaction section shown in FIG.
  • the amount of dissolved oxygen that was deaerated using a membrane deaerator having a hollow fiber membrane instead of the ion exchange water used for the preparation of the raw material liquid 1 and the raw material liquid 2 A dispersion containing vanadium dioxide-containing particles 33 and water was prepared in the same manner except that 4.0 mg / L of degassed water was used.
  • vanadium dioxide-containing particles 43 to 45 In the preparation of the vanadium dioxide-containing particles 33 to 35, vanadium dioxide was similarly obtained except that formic acid was added to the raw material liquid 1 and the raw material liquid 2 under the condition of 0.15% by mass as a reducing compound. Each dispersion containing the contained particles 43 to 45 was prepared.
  • the raw material liquid 1 containing ammonium vanadate (V) is fed from the raw material liquid container 1 (5) through the flow path (6) by a pump (7), and heated by a heating medium (15) at 75 ° C. and 30 MPa. Heating and pressing were performed so as to satisfy the conditions.
  • the raw material liquid 2 containing hydrazine hydrate is fed from the raw material liquid container 2 (2) through the flow path (3) by the pump (4), and heated by the heating medium (13) at 440 ° C. and 30 MPa.
  • Supercritical water was obtained by heating and pressing under conditions. All the water used for preparation of the raw material liquid 1 and the raw material liquid 2 was ion-exchanged water (dissolved oxygen amount: 8.1 mg / L).
  • the reaction solution 85 was formed by mixing under the following conditions, and the solution was sent to the hydrothermal reaction section (16), which is a hydrothermal reaction section. In the hydrothermal reaction part, it sent to the heating part piping (17) arrange
  • the treatment time (passage time) was 2 seconds under the conditions of 400 ° C. and 30 MPa, and the vanadium dioxide (VO 2 ) -containing particles 46 were formed. Subsequently, the reaction liquid 46 was cooled in the cooling part (8), and the dispersion liquid containing the vanadium dioxide containing particle
  • the amount of dissolved oxygen subjected to deaeration treatment using a membrane deaerator having a hollow fiber membrane instead of the ion exchange water used for the preparation of the raw material liquid 1 and the raw material liquid 2 A dispersion containing vanadium dioxide-containing particles 47 and water was prepared in the same manner except that 4.0 mg / L of degassed water was used.
  • vanadium dioxide-containing particles 55 to 56 In the preparation of the vanadium dioxide-containing particles 47 to 48, vanadium dioxide was similarly obtained except that formic acid was added to the raw material liquid 1 and the raw material liquid 2 under the condition of 0.15% by mass as a reducing compound. Each dispersion containing the contained particles 55 to 56 was prepared.
  • thermochromic TC1 As is clear from the results shown in Table IV, a comparison was made by applying a reaction solution composed of ammonium vanadate (V), a reducing agent and degassed water to a hydrothermal reaction using a flow reactor.
  • V ammonium vanadate
  • a reducing agent As compared with the example, it can be seen that the thermochromic TC1 and the thermochromic decrease rate ⁇ T after the forced deterioration treatment are low.
  • the vanadium dioxide (VO 2 ) -containing particles prepared under the production condition 1 (embodiment 1) according to the present invention have a smaller average particle diameter (D) than that of the comparative example and have a polydispersity index (PDI). It was proved that the particle size distribution was small and the thermochromic property was excellent.
  • Example 3 and Example 4 that demonstrate the specific effects of Production Condition 2 (Embodiment 2) according to the present invention are shown below.
  • Example 3 Preparation of vanadium dioxide-containing particles >> [Preparation of vanadium dioxide-containing particles 101: comparative example] Dissolve 19.0 g of vanadium oxide sulfate (IV) (VOSO 4 ) in ion-exchanged water to 300 mL, and while stirring this solution, add 68 g of 3.0 mol / L NH 3 aqueous solution as an alkali to adjust the pH to 8 Reaction solution 1 was prepared as 0.0. This reaction liquid 1 was put into an autoclave having an internal volume of 500 mL, and subjected to a hydrothermal reaction treatment at 250 ° C. and 3.98 MPa for 8 hours to form vanadium dioxide (VO 2 ) -containing particles 101. Next, the reaction liquid was cooled to prepare a dispersion liquid containing vanadium dioxide-containing particles 101.
  • IV vanadium oxide sulfate
  • VOSO 4 vanadium oxide sulfate
  • a raw material liquid container 1 (5) shown in FIG. 2 19.0 g of vanadium oxide (IV) (VOSO 4 ) was dissolved in ion-exchanged water to 300 mL, and 3.0 mol as an alkali while stirring this liquid. 68 mL of / L NH 3 aqueous solution was added to prepare a raw material liquid 1 having a pH of 8.0. On the other hand, ion exchange water was stored as the raw material liquid 2 in the raw material liquid container 2 (2) shown in FIG.
  • IV vanadium oxide
  • the raw material liquid 1 containing vanadium oxide sulfate (IV) and alkali is fed from the raw material liquid container 1 (5) through the flow path (6) by a pump (7), and heated at 25 ° C. with a heating medium (15). Pressurization was performed so that the condition was 30 MPa.
  • the ion exchange water as the raw material liquid 2 is fed from the raw material liquid container 2 (2) through the flow path (3) by the pump (4), and is heated by the heating medium (13) at 440 ° C. and 30 MPa. Was heated and pressurized to obtain supercritical water.
  • the raw material liquid 1 containing vanadium oxide (IV) oxide and alkali and the raw material liquid 2 which is supercritical water at the junction (MP) shown in FIG. The mixture was mixed under the conditions of 4 to form a reaction liquid 2, which was fed to the hydrothermal reaction section (16) which is a hydrothermal reaction section. In the hydrothermal reaction part, it sent to the heating part piping (17) arrange
  • the hydrothermal reaction conditions in the heating pipe section (17) are 270 ° C. and 10 MPa, the treatment time (passing time) is 2 seconds, and the Reynolds number Re of the reaction liquid 2 in the heating section pipe (17) is 500.
  • the vanadium dioxide (VO 2 ) -containing particles 102 were formed. Subsequently, the reaction liquid 2 was cooled in the cooling part (8), and the dispersion liquid containing the vanadium dioxide containing particle
  • Embodiment 2A Preparation of Vanadium Dioxide-Containing Particles 108-131: Present Invention (Embodiment 2A)]
  • the line length L and the flow rate in the hydrothermal reaction section are appropriately changed for the preparation of the vanadium dioxide-containing particles 105 to 107, and the reaction solution is treated.
  • Dispersions containing vanadium dioxide-containing particles 108 to 131 were prepared in the same manner except that the times were changed to 3 seconds, 5 seconds, 12 seconds, 50 seconds, 100 seconds, 300 seconds, 700 seconds, and 1000 seconds, respectively. did.
  • the raw material liquid 1 containing vanadium oxide sulfate (IV) is fed from the raw material liquid container 1 (5) through the flow path (6) by a pump (7), and heated by a heating medium (15) at 25 ° C. and 30 MPa. Pressurization was performed to satisfy the conditions.
  • the raw material liquid 2 containing sodium hydroxide as the raw material liquid 2 is fed from the raw material liquid container 2 (2) through the flow path (3) by the pump (4), and is heated to 440 ° C. by the heating medium (13).
  • supercritical water was obtained by heating and pressing under the condition of 30 MPa.
  • the raw material liquid 1 containing vanadium oxide (IV) oxide at the junction (MP) shown in FIG. 2 and the raw material liquid 2 that is supercritical water containing alkali are subjected to the conditions that the pH of the reaction liquid becomes 8.0.
  • the mixture was mixed to form a reaction liquid 35, which was sent to the hydrothermal reaction section (16), which is a hydrothermal reaction section.
  • the processing time (passage time) is 2 seconds under the conditions of 400 ° C. and 30 MPa, and the Reynolds number Re of the reaction liquid 2 in the heating section pipe (17) is 2000.
  • vanadium dioxide (VO 2 ) -containing particles were formed.
  • the reaction liquid 135 was cooled in the cooling unit (8) to prepare a dispersion liquid containing vanadium dioxide-containing particles 135 and water.
  • the hydrodynamic diameter (nm) was measured by a dynamic light scattering (DLS) method using a dynamic light scattering analyzer (DLS-8000, manufactured by Otsuka Electronics Co., Ltd.). And based on this, the average particle diameter of the particle size distribution by cumulant analysis was calculated
  • D average particle diameter
  • the polydispersity index (PDI) is a numerical value calculated on the assumption that the particle size distribution is a normal distribution in the cumulant analysis measured by the dynamic light scattering method (DLS method) in the same manner as the measurement of the average particle size (D). did.
  • thermochromic properties evaluation of thermochromic properties (TC1) immediately after preparation)
  • the dispersion liquid containing each vanadium dioxide-containing particle prepared above was filtered at a flow rate of 300 mL / min and a hydraulic pressure of 0.1 MPa using Vivaflow 50 (effective filtration area 50 cm 2 , fractional molecular weight 5000) manufactured by Sartorius steady. Concentration adjustment is performed, and vanadium dioxide-containing particles are added to polyvinyl alcohol so that the ratio of vanadium dioxide-containing particles to the total mass of polyvinyl alcohol and vanadium dioxide-containing particles is 10% by mass to prepare a coating solution. did.
  • the film for measurement 1 is formed by coating and drying on a 50 ⁇ m-thick polyethylene terephthalate (PET) substrate manufactured by Teijin-Dupont Film Co., Ltd. and forming a layer containing vanadium dioxide-containing particles having a dry film thickness of 3 ⁇ m. Produced.
  • PET polyethylene terephthalate
  • thermochromic property TC1 (%) immediately after preparation was evaluated according to the following method.
  • the transmittance at a wavelength of 2000 nm (T 25 ° C. ) in an environment of 25 ° C. and 50% RH and the transmittance at a wavelength of 2000 nm (T 85 ° C. ) in an environment of 85 ° C. and 50% RH.
  • Measurement was performed to determine a transmittance difference 1 (T 85 ° C.- T 25 ° C. ) immediately after preparation, and this was evaluated according to the following criteria as a measure of thermochromic properties (TC1) immediately after preparation.
  • the measurement was performed by attaching a temperature control unit (manufactured by JASCO Corporation) to a spectrophotometer V-670 (manufactured by JASCO Corporation).
  • Transmittance difference 1 (T 85 ° C.- T 25 ° C. ) is 50% or more 4: Transmittance difference 1 (T 85 ° C.- T 25 ° C. ) is 45% or more and less than 50% 3: Transmittance difference 1 (T 85 ° C. ⁇ T 25 ° C. ) is 35% or more and less than 45% 2: Transmittance difference 1 (T 85 ° C. ⁇ T 25 ° C. ) is 25% or more and less than 35% 1: Transmittance difference 1 (T 85 ° C. ⁇ T 25 ° C.
  • the dispersion containing the vanadium dioxide-containing particles subjected to the forced deterioration treatment was flowed at 300 mL / min with a flow rate of 0 using a Vivaflow 50 (effective filtration area 50 cm 2 , molecular weight cut-off 5000) manufactured by Sartorius steady.
  • the concentration is adjusted by filtration at 1 MPa so that the vanadium dioxide-containing particles in polyvinyl alcohol have a ratio of vanadium dioxide-containing particles to 10% by mass with respect to the total mass of polyvinyl alcohol and vanadium dioxide-containing particles.
  • the film for measurement 2 in which a layer containing vanadium dioxide containing particles having a dry film thickness of 3 ⁇ m was formed by applying and drying onto a 50 ⁇ m-thick polyethylene terephthalate (PET) substrate manufactured by Teijin-Dupont Film Co., Ltd. did.
  • PET polyethylene terephthalate
  • ⁇ Measurement of transmittance decrease width ⁇ T> The reduction width ⁇ T (%) of the transmittance difference 2 (T 85 ° C.- T 25 ° C. ) after the forced deterioration treatment with respect to the transmittance difference 1 (T 85 ° C.- T 25 ° C. ) immediately after the preparation as measured above is obtained by the following equation. This was evaluated according to the following criteria as a measure of durability.
  • Reduced transmittance ⁇ T (%) [(transmittance difference 1 immediately after preparation (T 85 ° C. ⁇ T 25 ° C. ) ⁇ Transmittance difference 2 after forced deterioration treatment (T 85 ° C. ⁇ T 25 ° C. )) / Preparation Transmittance difference 1 immediately after (T 85 ° C.- T 25 ° C. )] ⁇ 100
  • the transmittance decrease width ⁇ T is less than 5.0% 4: The transmittance decrease width ⁇ T is 5.0% or more and less than 15% 3: The transmittance decrease width ⁇ T is 15% The ratio is less than 20%.
  • the transmittance decrease width ⁇ T is 20% or more and less than 25%.
  • the transmittance decrease width ⁇ T is 25% or more. Shown in VII.
  • the reaction solution composed of vanadium oxide (IV) sulfate and alkali was treated in the hydrothermal reaction time range defined in the present invention. It can be seen that the rate of decrease in thermochromic properties after the thermochromic properties and forced deterioration treatment is low compared to the comparative example.
  • the vanadium dioxide (VO 2 ) -containing particles prepared under the production condition 2 (Embodiment 2) according to the present invention have a smaller average particle diameter (D) than that of the comparative example, and have a polydispersity index (PDI). It was proved that the particle size distribution was small and the thermochromic property was excellent.
  • Example 4 Preparation of vanadium dioxide-containing particles >> [Preparation of Vanadium Dioxide-Containing Particles 151: Comparative Example]
  • Ammonium vanadate (V) (NH 4 VO 3 , manufactured by Wako Pure Chemical Industries, Ltd., special grade) 7.1 g was dissolved in 326.0 g of ion-exchanged water at 60 ° C., and this solution was stirred with 0.95 mol. 16.9 g of / L hydrazine hydrate (N 2 H 4 .H 2 O, Wako Pure Chemical Industries, Ltd., special grade) was slowly added dropwise until pH 9.5 was reached.
  • This reaction solution 151 was placed in an autoclave having an internal volume of 500 mL, and subjected to a hydrothermal reaction treatment at 250 ° C. and 3.98 MPa for 12 hours to form vanadium dioxide (VO 2 ) -containing particles 151. Next, the reaction liquid was cooled to prepare a dispersion liquid containing vanadium dioxide-containing particles 151.
  • VO 2 vanadium dioxide
  • the raw material liquid 1 containing ammonium vanadate (V) and hydrazine hydrate is fed from the raw material liquid container 1 (5) through the flow path (6) by the pump (7), and heated by the heating medium (15). It heated and pressurized so that it might become the conditions of 30 Mpa at ° C.
  • the ion exchange water as the raw material liquid 2 is fed from the raw material liquid container 2 (2) through the flow path (3) by the pump (4), and is heated by the heating medium (13) at 440 ° C. and 30 MPa. Was heated and pressurized to obtain supercritical water.
  • the hydrothermal reaction conditions in the heating pipe section (17) are 270 ° C. and 10 MPa, the treatment time (passing time) is 2 seconds, and the Reynolds number Re of the reaction liquid 2 in the heating section pipe (17) is 500.
  • the vanadium dioxide (VO 2 ) -containing particles 152 were formed. Subsequently, the reaction liquid 2 was cooled in the cooling part (8), and the dispersion liquid containing the vanadium dioxide containing particle
  • the raw material liquid 1 containing ammonium vanadate (V) is fed from the raw material liquid container 1 (5) through the flow path (6) by a pump (7), and heated by a heating medium (15) at 75 ° C. and 30 MPa. Pressurization was performed to satisfy the conditions.
  • the raw material liquid 2 containing hydrazine hydrate is fed from the raw material liquid container 2 (2) through the flow path (3) by the pump (4), and heated by the heating medium (13) at 440 ° C. and 30 MPa. Supercritical water was obtained by heating and pressing under conditions.
  • the reaction solution 185 was formed by mixing under the conditions described above, and the solution was sent to the hydrothermal reaction section (16) which is a hydrothermal reaction section. In the hydrothermal reaction part, it sent to the heating part piping (17) arrange
  • the processing time (passage time) is 2 seconds under the conditions of 400 ° C. and 30 MPa, and the Reynolds number Re of the reaction liquid 2 in the heating section pipe (17) is 2000.
  • vanadium dioxide (VO 2 ) -containing particles 185 were formed. Subsequently, the reaction liquid 85 was cooled in the cooling part (8), and the dispersion liquid containing the vanadium dioxide containing particle
  • vanadium dioxide-containing particles 194 comparative example
  • the vanadium dioxide-containing particles 194 were prepared in the same manner except that the treatment time (passage time) in the hydrothermal reaction section (16), which is a hydrothermal reaction section, was changed to 2000 seconds. did.
  • the reaction liquid composed of ammonium vanadate (V) and the reducing agent is treated in the hydrothermal reaction time range defined in the present invention using a flow reactor.
  • the thermochromic property and the rate of decrease in thermochromic property after the forced deterioration treatment are lower than those of the comparative example.
  • the vanadium dioxide (VO 2 ) -containing particles prepared under the production condition 2 (Embodiment 2) according to the present invention have a smaller average particle diameter (D) than that of the comparative example, and have a polydispersity index (PDI). It was proved that the particle size distribution was small and the thermochromic property was excellent.
  • Example 5 that demonstrates the specific effect of Production Condition 3 (Embodiment 3) according to the present invention is shown below.
  • Preparation of vanadium dioxide-containing particles >> [Preparation of vanadium dioxide-containing particles 201] (Desalting treatment of slurry raw material liquid 1) As raw material liquid 1, 19.0 g of vanadium oxide sulfate (IV) (VOSO 4 ) was dissolved in ion-exchanged water to 300 mL, and 68 mL of 3.0 mol / L NH 3 aqueous solution was added as an alkali while stirring this liquid. Thus, a slurry raw material liquid 1 having a pH of 8.0 was prepared.
  • V vanadium oxide sulfate
  • the slurry raw material liquid (52, initial electrical conductivity: 30000 ⁇ S / m) is stored in the adjustment kettle (51), and is circulated by using the circulation pump (54). Water containing salts in the liquid is discharged from the discharge port (56) at a discharge amount V1, and then ultrafiltered from the ion exchange water stock kettle (57) via the ion exchange water supply line (59). Ion exchange water (58) having the same capacity as the discharge amount V1 in the part (55) was added at the addition amount V2.
  • Vanadium dioxide-containing particles 201 were prepared according to the following method using the flow reactor having the hydrothermal reaction section shown in FIGS. 2 and 6.
  • the raw material liquid container 1 (5) shown in FIG. 2 contains the vanadium oxide sulfate (IV) subjected to the desalting treatment by the above method and the alkali as the raw material liquid 1, and has an electric conductivity ( ⁇ S / m) of 1000 ⁇ S / m.
  • the slurry raw material liquid 1 which is m was accommodated.
  • ion exchange water was stored as the raw material liquid 2 in the raw material liquid container 2 (2) shown in FIGS.
  • the slurry raw material liquid containing vanadium oxide oxide (IV) and alkali is fed from the raw material liquid container 1 (5) through the flow path (6) by the pump (7), and heated at 25 ° C. with the heating medium (15). Pressurization was performed so that the condition was 30 MPa.
  • the ion exchange water as the raw material liquid 2 is fed from the ion exchange water container (2) through the flow path (3) by the pump (4), and is heated by the heating medium (13) at 440 ° C. and 30 MPa. Was heated and pressurized to obtain supercritical water.
  • vanadium dioxide-containing particles 202 prepared in the same manner except that the desalting treatment 2 by the ultrafiltration method of the slurry raw material liquid described below was performed.
  • vanadium dioxide-containing particles 204 were prepared in the same manner except that the slurry raw material liquid was changed to the desalting treatment 4 as the centrifugal separation treatment.
  • Desalination treatment 4 After performing solid-liquid separation by centrifugation treatment on the slurry raw material liquid using a known centrifuge, a part of the aqueous separation liquid is discharged out of the system, and then the same volume of ion exchange as discharged Water was additionally added, and then a dispersion treatment was performed. This operation was repeated to discharge unnecessary salts, and the electrical conductivity of the slurry raw material liquid was adjusted to 500 ⁇ S / m.
  • A K ⁇ / ⁇ cos ⁇
  • A is the average crystallite diameter
  • K is the Scherrer constant
  • ⁇ is the X-ray wavelength
  • ⁇ is the half width of the diffraction line.
  • ⁇ is the Bragg angle with respect to the diffraction line.
  • the average crystallite size is 15 nm or more and 40 nm or less ⁇ : The average crystallite size is less than 15 nm or exceeds 40 nm [Measurement of average primary particle size]
  • the dispersion liquid containing each vanadium dioxide-containing particle and water prepared above was dried and solidified in an oven at 120 ° C. to obtain a powder, and a particle sample for measurement was prepared.
  • an SEM photograph was taken with a scanning electron microscope (Hitachi, Model S-5000).
  • the particle diameter was calculated using the photographed SEM photograph (1100 nm ⁇ 950 nm).
  • the particle diameter of the vanadium dioxide-containing particles is the same as the diameter of the vanadium dioxide-containing particles.
  • the diameter of the vanadium dioxide-containing particles is the same as the diameter of the vanadium dioxide-containing particles. did.
  • 30 particles having the most universal size and shape were selected, the average primary particle size of 30 particles was calculated, and the average value was defined as the average primary particle size (D) (nm).
  • the average primary particle size is 15 nm or more and 40 nm or less ⁇ : The average primary particle size is more than 40 nm and less than 100 nm XX: The average primary particle size is more than 100 nm The results are shown in Table XI.
  • a vanadium dioxide-containing particle-containing layer coating solution 201 having the following composition was prepared.
  • Dispersion containing vanadium dioxide-containing particles 301 40 parts by weight Beam set 577 (manufactured by Arakawa Chemical Co., Ltd.) 30 parts by weight Irgacure 127 (manufactured by BASF Corporation) 1 part by weight MegaFuck F-552 (manufactured by DIC Corporation) Ketone diluent (1% by mass) 2 parts by mass Methyl isobutyl ketone 27 parts by mass [Preparation of optical films 202 to 204] Optical films 202 to 204 were produced in the same manner as in the production of the optical film 201 except that the vanadium dioxide-containing particles 202 to 204 were used in place of the vanadium dioxide containing particles 201, respectively.
  • thermochromic evaluation was performed according to the following method.
  • the transmittance at a wavelength of 2000 nm (T 25 ° C. ) in an environment of 25 ° C. and 50% RH and the transmittance at a wavelength of 2000 nm (T 85 ° C. ) in an environment of 85 ° C. and 50% RH.
  • the transmittance difference (T 85 ° C.- T 25 ° C. ) was determined and classified according to the following criteria, which was used as a measure of thermochromic properties. The measurement was performed by attaching a temperature control unit (manufactured by JASCO Corporation) to a spectrophotometer V-670 (manufactured by JASCO Corporation).
  • Transmittance difference is 70% or more
  • Transmittance difference is 50% or more and less than 70%
  • Transmittance difference is 40% or more and less than 50%
  • Transmittance difference is 25% or more
  • Haze is less than 2.0% ⁇ ⁇ : Haze is 2.0% or more and less than 3.0% ⁇ : Haze is 3.0% or more and less than 5.0% ⁇ : 5.0% or more
  • Table XII The results obtained as described above are shown in Table XII.
  • the average primary particle size of the vanadium oxide-containing particles is in the range of 15 to 40 nm by subjecting the slurry raw material liquid containing the vanadium-containing compound to a desalting treatment before the hydrothermal reaction.
  • the average crystallite diameter can be set within a range of 15 to 40 nm.
  • Example 6 that demonstrates the specific effect of Production Condition 4 (Embodiment 4) according to the present invention is shown below.
  • Vanadium dioxide-containing particles 301 to 330 were prepared as follows.
  • the slurry raw material liquid 1 containing vanadium oxide sulfate (IV) and alkali is fed from the raw material liquid container 1 (5) through the flow path (6) by a pump (7), and heated at 25 ° C. with a heating medium (15). , And pressurized so as to satisfy the condition of 30 MPa.
  • ion exchange water as the raw material liquid 2 is fed from the raw material liquid container 2 (2) through the flow path (3) by a pump (4), and heated by a heating medium (13) at 440 ° C. and 30 MPa. Was heated and pressurized to obtain supercritical water.
  • slurry raw material liquid 1 containing vanadium oxide sulfate (IV) and alkali at the confluence (MP) and raw material liquid 2 which is supercritical water are used as a volume ratio
  • slurry raw material liquid 1: raw material liquid 2 1:
  • the reaction solution 1 was prepared by mixing under the conditions of 4 and fed to the hydrothermal reaction section (16) which is a hydrothermal reaction section.
  • the reaction liquid 1 was sent to the heating part piping (17) arrange
  • the hydrothermal reaction in the heating section pipe (17) is performed under the conditions of 400 ° C.
  • the treatment time passesing time
  • the vanadium dioxide (VO 2 ) -containing particles 201 are obtained as the reaction liquid 2. It was. Subsequently, the reaction liquid 2 was cooled in the cooling part (8), and the dispersion liquid containing the vanadium dioxide containing particle
  • the prepared dispersion was filtered, and the residue was washed with water and ethanol. Further, this residue was dried at 60 ° C. for 10 hours using a constant temperature dryer to prepare vanadium dioxide-containing particles 301.
  • vanadium dioxide-containing particles 302 to 304 In the preparation of the vanadium dioxide-containing particles 301, vanadium dioxide was similarly prepared except that the slurry raw material liquids 2 to 4 prepared as follows were added to the raw material liquid container 1 (5) instead of the slurry raw material liquid 1. Containing particles 302-304 were prepared.
  • the slurry raw material liquids 2 to 4 were prepared by subjecting 200 mL of this slurry raw material liquid to ultrasonic dispersion treatment for 30 seconds, 60 seconds and 120 seconds, respectively, using an ultrasonic disperser (UH150, manufactured by SMT). .
  • Vanadium dioxide-containing particles 305 were produced in the same manner as in the preparation of the vanadium dioxide-containing particles 301 except that the slurry raw material liquid 5 prepared as follows was used instead of the slurry raw material liquid 1.
  • vanadium oxide sulfate (IV) (VOSO 4 ) was dissolved in 300 mL of ion-exchanged water, and while stirring this solution, the glycine aqueous solution was added to glycine with respect to the total mass of vanadium oxide (IV) sulfate. Was added so that the mass was 10 mass%, and chemical dispersion was performed. Furthermore, 68 mL of a 3.0 mol / L NH 3 aqueous solution was added as an alkali to adjust the pH at a liquid temperature of 25 ° C. to 8.0.
  • the slurry raw material liquid 5 was prepared by subjecting 200 mL of this slurry raw material liquid to an ultrasonic dispersion treatment for 120 seconds using an ultrasonic dispersing machine (UH150, manufactured by SMT).
  • vanadium dioxide-containing particles 306 to 309 In the preparation of the vanadium dioxide-containing particles 305, glycine, which is a dispersant used in the preparation of the slurry raw material liquid 5, is L ( ⁇ )-threonine (manufactured by Wako Pure Chemical Industries, Ltd.), sarcosine (Wako Pure Chemical Industries, Ltd. ( ), L-alanine (manufactured by Wako Pure Chemical Industries, Ltd.), and polyvinylpyrrolidone K 90 (abbreviation: PVP Wako Pure Chemical Industries, Ltd.), respectively.
  • the vanadium dioxide-containing particles 306 to 309 were prepared in the same manner except that these slurry raw material liquids 6 to 9 were used instead of the slurry raw material liquid 5, respectively.
  • Vanadium dioxide-containing particles 310 to 312 were prepared in the same manner as in the preparation of the vanadium dioxide-containing particles 301 except that slurry raw material liquids 10 to 12 prepared by the following method were used instead of the slurry raw material liquid 1.
  • the slurry raw material liquid is subjected to high-pressure dispersion by applying nanocycle (C-ES, manufactured by Yoshida Kikai Kogyo Co., Ltd.), a high-speed and high-pressure microreactor, and applying 1 cycle, 2 cycles, and 3 cycles, respectively, at a discharge pressure of 200 MPa. Treatment was performed to obtain slurry raw material liquids 10 to 12.
  • C-ES nanocycle
  • a high-speed and high-pressure microreactor a high-speed and high-pressure microreactor
  • Vanadium dioxide-containing particles 313 were prepared in the same manner as in the preparation of the vanadium dioxide-containing particles 301 except that the slurry raw material liquid 13 prepared according to the following method was used instead of the slurry raw material liquid 1.
  • vanadium oxide sulfate (IV) (VOSO 4 ) was dissolved in 300 mL of ion-exchanged water. While stirring this solution, the aqueous glycine solution was mixed with glycine with respect to the mass of vanadium oxide sulfate (IV). Chemical dispersion treatment was performed by adding so that the mass became 10 mass%. Further, 68 mL of a 3.0 mol / L NH 3 aqueous solution was added as an alkali to adjust the pH at a liquid temperature of 25 ° C. to 8.0 to prepare a slurry raw material liquid.
  • IV vanadium oxide sulfate
  • the slurry raw material liquid 13 was subjected to high-pressure dispersion treatment for 3 cycles at a discharge pressure of 200 MPa using Nanothe (C-ES, manufactured by Yoshida Kikai Kogyo Co., Ltd.), which is a high-speed and high-pressure microreactor.
  • vanadium dioxide-containing particles 318 to 320 were prepared in the same manner except that the slurry raw material liquids 18 to 20 prepared by the following method were used in place of the slurry raw material liquid 1.
  • slurry raw material liquids 18 to 20 19.0 g of vanadium oxide sulfate (IV) (VOSO 4 ) was dissolved in 300 mL of ion-exchanged water, and while stirring this solution, 68 mL of 3.0 mol / L NH 3 aqueous solution was added as an alkali.
  • a slurry raw material solution was prepared at a pH of 8.0. 30% by mass of ZrO 2 beads (diameter: 15 ⁇ m) are filled into this slurry raw material liquid, and a paint shaker (paint conditioner, manufactured by RED DEVIL) is used as a media type dispersing machine for 30 minutes, 60 minutes, respectively. For 90 minutes, the media was dispersed to obtain slurry raw material solutions 18-20.
  • a paint shaker paint conditioner, manufactured by RED DEVIL
  • vanadium dioxide-containing particles 321 were prepared in the same manner except that the slurry raw material liquid 21 prepared by the following method was used instead of the slurry raw material liquid 1.
  • vanadium oxide sulfate (IV) (VOSO 4 ) was dissolved in 300 mL of ion-exchanged water. While stirring this solution, the aqueous glycine solution was mixed with glycine with respect to the mass of vanadium oxide sulfate (IV). Chemical dispersion was carried out by adding so that the mass was 10% by mass. Furthermore, 68 mL of a 3.0 mol / L NH 3 aqueous solution was added as an alkali, and a slurry raw material liquid was prepared at a pH of 8.0 at a liquid temperature of 25 ° C. A 30 mass% ZrO 2 was prepared with respect to this slurry raw material liquid. Beads (diameter 15 ⁇ m) were filled, and media dispersion treatment was performed by operating for 90 minutes using a paint shaker (paint conditioner, manufactured by RED DEVIL), to obtain a slurry raw material liquid 21.
  • a paint shaker paint conditioner, manufactured by RED DE
  • vanadium dioxide-containing particles 326 were prepared in the same manner except that the slurry raw material liquid 26 prepared by the following method was used instead of the slurry raw material liquid 1.
  • glycine which is a dispersant used in the preparation of the slurry raw material liquid 26 is L ( ⁇ )-threonine (manufactured by Wako Pure Chemical Industries, Ltd.), sarcosine (Wako Pure Chemical Industries, Ltd.).
  • the dispersed particle size of the vanadium-containing compound contained in each of the slurry raw material liquids 2 to 30 subjected to each dispersion treatment was measured by the following method before the hydrothermal reaction.
  • the slurry raw material liquid 1 was measured in an undispersed state.
  • an average particle size is obtained by a dynamic light scattering (Dynamic Light Scattering: DLS) method using a dynamic light scattering analyzer (Zetasizer Nano S manufactured by Malvern), and this value is dispersed.
  • the particle size was taken.
  • the measurement conditions are as follows.
  • the particle diameter (area equivalent circle diameter) was calculated using an SEM photograph (1250 nm ⁇ 850 nm). In the SEM photograph, the area of each particle was measured, and the diameter of a circle having the same area was taken as the particle diameter. In the SEM photograph, 30 particles having the most universal size and shape were selected, and the average particle diameter of 30 particles was calculated. The particle size range was divided every 5 nm, a histogram was created, this distribution was defined as the particle size distribution, and the particle size distribution width was evaluated according to the following evaluation criteria.
  • haze (%) was measured using the haze meter (Nippon Denshoku Industries Co., Ltd. make, NDH2000) at room temperature (25 degreeC), and it evaluated according to the following evaluation criteria. .
  • Haze is 2.0% or less ⁇ : Haze is greater than 2.0% and 3.0% or less ⁇ : Haze is greater than 3.0% and 4.0% or less ⁇ : Haze is 4 Greater than 0% (Preparation of optical film)
  • a coating solution for forming an optical functional layer having the following composition is applied using a die coater so that the dry film thickness is 1.5 ⁇ m. The amount was adjusted and wet coating was performed, followed by drying at 90 ° C. for 1 minute.
  • ⁇ Coating liquid for optical functional layer formation Vanadium dioxide-containing particle dispersion (solvent: water) 9.3 parts by mass Resin binder (poly-N-vinylacetamide, trade name: GE191-103, Showa Denko KK, molecular weight 900000) 90.7 parts by mass Each of the above components The materials were sequentially added, mixed and dissolved, and diluted with water to a solid content concentration of 3% by mass to prepare an aqueous optical functional layer forming coating solution.
  • solvent water
  • Resin binder poly-N-vinylacetamide, trade name: GE191-103, Showa Denko KK, molecular weight 900000
  • TSER Thermal barrier
  • the spectrophotometer (using an integrating sphere, manufactured by Hitachi, Ltd., U-4000 type) was used to measure the light transmittance and light reflectance every 2 nm in the region of 300 to 2500 nm. The measurement was performed under conditions of a low temperature (10 ° C.) and a high temperature (70 ° C.).
  • the vanadium dioxide-containing particles of the present invention are superior in dispersion particle size, particle size distribution width, and optical film haze and ⁇ TSER compared to the vanadium dioxide-containing particles of the comparative example. It was confirmed that
  • the particle size distribution width of the vanadium dioxide-containing particles 301 as a comparative example has a wide particle size distribution up to 95 nm as shown in FIG. 8, whereas the particle size of the vanadium dioxide-containing particles 311 of the present invention.
  • the end of the particle size distribution is 40 nm or less as shown in FIG. 9, and the particle size of the vanadium dioxide-containing particles subjected to the dispersion treatment before the hydrothermal reaction using a flow reactor is used. It can be seen that the distribution width is narrow.
  • a slurry raw material liquid that has been subjected to a dispersion treatment using a flow reactor that has a step of preparing a slurry raw material liquid containing a vanadium-containing compound and water, a step of dispersing the slurry raw material liquid, and a hydrothermal reaction section.
  • the average particle size is small, the formation of aggregates is suppressed, the particle size distribution is narrow, the monodispersity and dispersion stability are excellent, and the thermochromic properties are excellent.
  • Vanadium-containing particles can be produced, and the vanadium dioxide-containing particles are large between the internal environment and the external environment, such as a building such as a house or a building, and a moving body such as a vehicle.
  • the present invention can be applied to an optical film having an excellent thermochromic property that is installed in a place where heat exchange occurs.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
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Abstract

La présente invention traite le problème de fournir un procédé de production de particules contenant du dioxyde de vanadium qui ont un petit diamètre de particule moyen et une distribution de diamètre de particule étroite, sont excellents en matière de monodispersion et de stabilité de dispersion, et ont d'excellentes propriétés thermochromiques. Le procédé de production de particules contenant du dioxyde de vanadium selon la présente invention consiste à utiliser un réacteur de type à écoulement traversant comprenant une partie de réaction hydrothermique et utiliser un mélange réactionnel liquide obtenu par mélange d'une boue de matière première, la boue comprenant un composé contenant du vanadium et de l'eau, et un composé qui réagit avec le composé contenant du vanadium, avec de l'eau dans un état supercritique ou sous-critique. Le procédé de production est caractérisé en ce que 1) l'eau est de l'eau dégazée, 2) le temps sur lequel le mélange réactionnel liquide passe à travers la partie de réaction hydrothermique est de 3 à 1000 secondes, 3) la suspension de matière première est soumise, avant la synthèse hydrothermique, à un traitement de dessalage pour l'élimination du sel de celui-ci, et par conséquent les particules ont un diamètre de particule moyen de 15 à 40 nm et un diamètre de cristallite moyen de 15 à 40 nm, ou 4) avant l'étape de production de particules contenant du dioxyde de vanadium, la suspension de matière première est soumise à un traitement de dispersion.
PCT/JP2017/019096 2016-05-30 2017-05-23 Procédé de production de particules contenant du dioxyde de vanadium WO2017208892A1 (fr)

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JP2020138871A (ja) * 2019-02-26 2020-09-03 国立研究開発法人産業技術総合研究所 二酸化バナジウム粒子の製造方法
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CN113087019B (zh) * 2021-05-12 2022-09-13 郑州大学 一种利用超临界流体技术制备铁磁性vo2的制备方法

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