WO2018110062A1 - 二酸化バナジウム含有粒子、サーモクロミックフィルム及び二酸化バナジウム含有粒子の製造方法 - Google Patents

二酸化バナジウム含有粒子、サーモクロミックフィルム及び二酸化バナジウム含有粒子の製造方法 Download PDF

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WO2018110062A1
WO2018110062A1 PCT/JP2017/037169 JP2017037169W WO2018110062A1 WO 2018110062 A1 WO2018110062 A1 WO 2018110062A1 JP 2017037169 W JP2017037169 W JP 2017037169W WO 2018110062 A1 WO2018110062 A1 WO 2018110062A1
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vanadium
range
vanadium dioxide
atom
containing particles
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PCT/JP2017/037169
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English (en)
French (fr)
Japanese (ja)
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山本　昌一
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コニカミノルタ株式会社
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Priority to CN201780076536.3A priority Critical patent/CN110072815B/zh
Priority to JP2018556215A priority patent/JP6973409B2/ja
Publication of WO2018110062A1 publication Critical patent/WO2018110062A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G7/00—Compounds of gold
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy

Definitions

  • the present invention relates to a vanadium dioxide-containing particle, a thermochromic film, and a method for producing a vanadium dioxide-containing particle. More specifically, the present invention relates to a vanadium dioxide-containing particle, a thermochromic film, and a vanadium dioxide that have excellent fastness to thermal expansion accompanying heating and cooling. The present invention relates to a method for producing contained particles.
  • thermochromic material a material having thermochromic properties
  • thermochromic material is a material whose optical properties such as transparent state / reflective state change reversibly with temperature.
  • thermochromic material when applied to a window glass of a building, for example, it can reflect sunlight in the summer to block heat, and in winter it can transmit sunlight and use heat, Both energy saving and comfort can be achieved.
  • thermochromic materials that has received the most attention is vanadium dioxide (VO 2 ) particles. It is known that vanadium dioxide particles exhibit thermochromic properties during a phase transition near room temperature. Therefore, by utilizing this property, thermochromic properties depending on the environmental temperature can be obtained.
  • VO 2 vanadium dioxide
  • vanadium dioxide has several polymorphs of crystal phases such as A phase, B phase, C phase and R phase, but the crystal structure exhibiting the thermochromic characteristics as described above has a rutile type. It is limited to the crystal phase (hereinafter referred to as “R phase”). Since this R phase has a monoclinic structure below the transition temperature, it is also called an M phase.
  • R phase the crystal phase
  • M phase the crystal phase
  • the particles in order to exhibit substantially excellent thermochromic properties, it is desirable that the particles do not have a metal that does not exhibit thermochromic properties or a crystalline phase other than the M phase of vanadium dioxide. .
  • the particle diameter of the vanadium dioxide particles is as uniform and small as possible (100 nm or less), the vanadium dioxide particles are not aggregated, and the particles are isotropic. It is desirable to have a different shape.
  • a technique for producing such particles a synthesis method using a hydrothermal reaction has been reported.
  • Patent Document 1 includes hydrazine (N 2 H 4 ) or a hydrate thereof (N 2 H 4 .nH 2 O) and water using divanadium pentoxide (V 2 O 5 ) or the like as a raw material.
  • vanadium dioxide (VO 2 ) single crystal fine particles obtained by hydrothermal reaction of a solution substantially free of titanium dioxide (TiO 2 ) particles are disclosed.
  • vanadium dioxide is doped with a specific element (elements having an atomic number of 21 to 30, or indium, antimony, tin, gallium, germanium, lead, or bismuth), so that the aspect ratio is 1: 1.
  • particles having a particle size of 100 nm or less can be obtained within a range of ⁇ 10: 1.
  • vanadium dioxide one or more elements selected from titanium (Ti), niobium (Nb), molybdenum (Mo), and tungsten (W), rhodium (Rh), palladium (Pd)
  • particles having a transition temperature sufficiently reduced to room temperature can be obtained by doping with one or more elements selected from ruthenium (Ru).
  • JP 2011-178825 A Chinese Patent Application No. 102120615 US Patent Application Publication No. 2012/0171472
  • the present invention has been made in view of the above problems and circumstances, and the solution is to produce vanadium dioxide-containing particles, thermochromic film, and vanadium dioxide-containing particles having excellent fastness to thermal expansion accompanying heating and cooling. Is to provide a method.
  • the present inventor in the process of examining the cause of the above problems, the element A whose Pauling electronegativity is within a specific range and the element whose Pauling electronegativity is within a specific range B is contained, the total content of element A is within a specific range with respect to vanadium (100 atom%), and the total content of element B is within a specific range.
  • the inventors have found that vanadium dioxide-containing particles, thermochromic film, and vanadium dioxide-containing particles can be produced with excellent fastness to expansion, and the present invention has been achieved.
  • Vanadium dioxide-containing particles having thermochromic properties
  • the total content of the element A is in the range of 0.5 to 20 atom% and the total content of the element B is in the range of 0.05 to 20 atom% with respect to vanadium (100 atom%).
  • Vanadium-containing particles Vanadium-containing particles.
  • the element B is tungsten;
  • the element B is molybdenum; 3.
  • the standard redox potential of the element A at 25 ° C. is in the range of ⁇ 0.45 to 0 V;
  • thermochromic film containing the vanadium dioxide-containing particles according to any one of items 1 to 4.
  • thermochromic film according to claim 5 which is maintained at a ratio of 60% or more of the difference in light transmittance before the cold heat treatment.
  • a method for producing vanadium dioxide-containing particles having thermochromic properties A vanadium-containing compound, an element A having a Pauling electronegativity in the range of 1.65 to 2.05, an element B having a Pauling electronegativity in the range of 2.10 to 2.54, and water.
  • a step of preparing a reaction solution comprising: Hydrothermal reaction of the reaction solution to form vanadium dioxide-containing particles; Have In the step of preparing the reaction solution, the total addition amount of the element A is in the range of 0.5 to 20 atom% with respect to vanadium (100 atom%), and the total addition amount of the element B is 0.05 to A method for producing vanadium dioxide-containing particles in a range of 20 atom%.
  • the vanadium dioxide-containing material according to item 7 or 8 wherein the hydrothermal reaction is performed within a liquid temperature range of 250 to 450 ° C. and within a reaction time of 1 second to 48 hours. Particle production method.
  • the vanadium dioxide-containing particles of the present invention include an element A having a Pauling electronegativity in the range of 1.65 to 2.05 and an element having a Pauling electronegativity in the range of 2.10 to 2.54.
  • B with respect to vanadium (100 atom%), the total content of element A is in the range of 0.5 to 20 atom%, and the total content of element B is in the range of 0.05 to 20 atom% It is characterized by being within.
  • element B for example, tungsten, molybdenum
  • element B has a higher electronegativity than vanadium (vanadium electronegativity: 1.63), so Hume Rosary's law (W.
  • Schematic which shows an example of the flow-type reaction apparatus which comprises the hydrothermal reaction part applicable to manufacture of the vanadium dioxide containing particle
  • the vanadium dioxide-containing particles of the present invention include an element A having a Pauling electronegativity in the range of 1.65 to 2.05 and an element having a Pauling electronegativity in the range of 2.10 to 2.54.
  • B with respect to vanadium (100 atom%), the total content of element A is in the range of 0.5 to 20 atom%, and the total content of element B is in the range of 0.05 to 20 atom% It is characterized by being within.
  • This feature is a technical feature common to the inventions according to the following embodiments.
  • the element B is tungsten, and the content of the tungsten is in the range of 0.5 to 10 atom% with respect to vanadium (100 atom%). It is preferable.
  • the element B is molybdenum and the molybdenum content is in the range of 0.5 to 10 atom% with respect to vanadium (100 atom%).
  • the standard redox potential of element A at 25 ° C. is in the range of ⁇ 0.45 to 0 V, and the content of element A is 0 with respect to vanadium (100 atom%). It is preferably in the range of 5 to 10 atom%.
  • the present invention can provide a thermochromic film containing the vanadium dioxide-containing particles.
  • thermochromic film of the present invention has a wavelength of 1300 nm under each condition of 15 ° C. and 70 ° C. after 4000 cycles of cold heat treatment, with treatment at 0 ° C. for 15 minutes and treatment at 85 ° C. for 15 minutes as one cycle. Is preferably maintained at a rate of 60% or more of the light transmittance difference before the cold heat treatment.
  • the present invention relates to a method for producing thermochromic vanadium dioxide-containing particles, comprising a vanadium-containing compound, an element A having a Pauling electronegativity in the range of 1.65 to 2.05, and a Pauling electricity
  • a step of preparing a reaction solution containing element B having a negative degree in the range of 2.10 to 2.54 and water, a step of hydrothermally reacting the reaction solution to form vanadium dioxide-containing particles In the step of preparing the reaction solution, the total addition amount of element A is within the range of 0.5 to 20 atom% and the total addition amount of element B is 0.05 to vanadium (100 atom%).
  • a method for producing vanadium dioxide-containing particles in the range of ⁇ 20 atom% can be provided.
  • the vanadium-containing compound is preferably a vanadium (IV) -containing compound.
  • the liquid temperature is in the range of 250 to 450 ° C.
  • the reaction time is in the range of 1 second to 48 hours. It is preferable to make it hydrothermally react.
  • ⁇ representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • thermochromic vanadium dioxide-containing particles of the present invention have a Pauling electronegativity in the range of 1.65 to 2.05 and a Pauling electronegativity of 2.10 to 2.54.
  • the element A is not particularly limited as long as it has a Pauling electronegativity in the range of 1.65 to 2.05, and may be used alone or in combination of two or more. It may be used. When two or more kinds are mixed and used, it is sufficient that the total content of the element A is in the range of 0.5 to 20 atom%.
  • Table I shows Pauling's electronegativity (Source: “Pauling Electronegativity”, Data takefrom James E Huhey; Inorganic Chemistry: Principles of structure 3 and Reactive 3; Reactive 3). Elements that are within the range of 2.05 are indicated.
  • the electronegativity of vanadium is 1.63.
  • the element A is preferably an element having a standard oxidation-reduction potential at 25 ° C. in the range of ⁇ 0.45 to 0 V.
  • the content at this time is 0 with respect to vanadium (100 atom%). It is preferably in the range of 5 to 10 atom%.
  • Table I shows the standard redox potential of element A (Source: “Chemical Handbook, Basic Edition”, Chemical Society of Japan, Maruzen, 1993, 4th revised edition).
  • Element B is not particularly limited as long as Pauling's electronegativity is in the range of 2.10 to 2.54, and may be used alone or in combination of two or more. It may be used. When two or more kinds are mixed and used, it is sufficient that the total content of the element B is in the range of 0.05 to 20 atom%. Table II shows elements whose Pauling electronegativity is in the range of 2.10 to 2.54.
  • the element B is preferably tungsten (W) or molybdenum (Mo), and more preferably tungsten and molybdenum are used in combination.
  • the preferable content of each is in the range of 0.5 to 10 atom% for tungsten and 0.5 to 10 atom% for molybdenum with respect to vanadium (100 atom%).
  • thermochromic properties As the thermochromic property of the vanadium dioxide-containing particles of the present invention, the difference in light transmittance at a wavelength of 1300 nm under conditions of 15 ° C. and 70 ° C. is preferably 10% or more, more preferably 30% or more. preferable.
  • the light transmittance difference can be calculated from the difference in light transmittance at a wavelength of 1300 nm measured at 15 ° C. and 70 ° C. for a film containing vanadium dioxide-containing particles.
  • the light transmittance is measured by attaching a temperature control unit (manufactured by JASCO Corporation) to a spectrophotometer V-670 (manufactured by JASCO Corporation).
  • the average particle size of the vanadium dioxide-containing particles is preferably in the range of 5 to 50 nm.
  • the average particle size of the vanadium dioxide-containing particles is measured with respect to 100 vanadium dioxide-containing particles by taking the particles with a scanning electron microscope, defining the diameter of a circle having an area equal to the projected area of the particles as the particle size, The arithmetic average value of these is calculated
  • the median diameter (D50) of the particle size distribution of the vanadium dioxide-containing particles is preferably 150 nm or less.
  • the median diameter (D50) of the particle size distribution of the vanadium dioxide-containing particles is determined by using each of the prepared dispersions after hydrothermal reaction (details will be described later) using a laser diffraction particle size distribution analyzer manufactured by Shimadzu Corporation. After dilution to a diffraction / scattered light intensity of 35 to 75% (absolute value 700 to 1500), the particle diameter D50 of the vanadium dioxide-containing particles can be measured as an index of particle diameter. The measured value uses a volume conversion value. The smaller the value of D50, the smaller the particle size.
  • the method for producing vanadium dioxide-containing particles of the present invention comprises a vanadium-containing compound, an element A having a Pauling electronegativity in the range of 1.65 to 2.05, and a Pauling electronegativity of 2.10 to 2
  • the total addition amount of element A is within the range of 0.5 to 20 atom% and the total addition amount of element B is within the range of 0.05 to 20 atom% with respect to vanadium (100 atom%). It is characterized by that.
  • grains which has the thermochromic property of this invention is demonstrated in detail.
  • Reaction liquid preparation step First, in the method for producing vanadium dioxide-containing particles of the present invention, a vanadium-containing compound, an element A having a Pauling electronegativity in the range of 1.65 to 2.05, and a polling A reaction solution containing element B having an electronegativity of 2.10 to 2.54 and water is prepared.
  • vanadium compounds examples include compounds containing pentavalent or tetravalent vanadium.
  • a compound containing pentavalent vanadium is used as the vanadium-containing compound, a reducing agent such as hydrazine (N 2 H 4 ) or a hydrate thereof (N 2 H 4 .nH 2 O) as described later is required. It becomes. Since these reducing agents have a strong reducing effect and are liable to cause overreduction, they cause a decrease in crystal regularity. Therefore, the vanadium-containing compound is preferably a tetravalent vanadium-containing compound.
  • Examples of pentavalent vanadium-containing compounds include divanadium pentoxide (V 2 O 5 ), ammonium vanadate (NH 4 VO 3 ), vanadium trichloride oxide (VOCl 3 ), and sodium vanadate. (NaVO 3 ) and the like.
  • Examples of tetravalent vanadium-containing compounds include vanadyl oxalate (VOC 2 O 4 ), vanadium oxide sulfate (VOSO 4 , hereinafter also referred to as vanadyl sulfate), and vanadium tetroxide (V 2 ).
  • the O 4) include those obtained by dissolving an acid such as sulfuric acid.
  • the vanadium-containing compound may be dissolved or dispersed in the raw material liquid.
  • a vanadium containing compound may be used individually by 1 type, and 2 or more types may be mixed and used for it. These compounds may be hydrated (hydrate).
  • the element A having a Pauling electronegativity in the range of 1.65 to 2.05 and the Pauling electronegativity of 2.10 to 2.54
  • the element B which is in the range is added.
  • the total amount of element A added is in the range of 0.5 to 20 atom% with respect to vanadium (100 atom%).
  • the total amount of element B added is in the range of 0.05 to 20 atom% with respect to vanadium (100 atom%).
  • a simple substance may be used, or a compound containing the element A or the element B may be used as long as the effect of the present invention is not impaired.
  • water Although the water which concerns on this invention is not specifically limited, The highly purified thing with few impurities is preferable, Specifically, purified water, such as ion-exchange water and distilled water, can be used.
  • a reducing agent When a pentavalent vanadium-containing compound is employed as the vanadium-containing compound according to the present invention, a reducing agent is used.
  • the reducing agent has a property of being easily dissolved in water, and may function as a reducing agent for pentavalent vanadium-containing compounds.
  • hydrazine such as hydrazine (N 2 H 4 ) and hydrazine monohydrate (N 2 H 4 ⁇ nH 2 O) and the like.
  • the reaction solution according to the present invention may be a mixture of substances having oxidizing properties or reducing properties.
  • An example of such a substance is hydrogen peroxide (H 2 O 2 ).
  • the pH of the reaction solution can be adjusted, or the vanadium-containing compound can be uniformly dissolved.
  • hydrogen peroxide hydrogen peroxide water (concentration 35 mass%, the Wako Pure Chemical Industries make, special grade) can be used suitably, for example.
  • the prepared reaction liquid is hydrothermally reacted to form vanadium dioxide-containing particles.
  • “reacting the reaction solution hydrothermally” means performing a hydrothermal reaction treatment on the reaction solution.
  • “Hydrothermal reaction” means that the temperature and pressure are in hot water (subcritical water) lower than the critical point of water (374 ° C., 22 MPa), or the temperature and pressure are higher than the critical point of water.
  • Subcritical water refers to water in a state where the temperature is in the range of 150 to 374 ° C. and the pressure is higher than the saturated water vapor pressure at that temperature.
  • a hydrothermal reaction process is implemented in an autoclave apparatus, for example.
  • a continuous method can be used in which a high pressure and high pressure water in a subcritical or supercritical state is mixed and synthesized using a flow type reactor (flow reactor) such as a pressure resistant tube type or tank type, and in particular, a tube.
  • a flow type reactor such as a pressure resistant tube type or tank type, and in particular, a tube.
  • a continuous process using a reactor of the type can be suitably used.
  • Hydrothermal reaction treatment conditions (amount of reactants, treatment temperature, treatment pressure, treatment time) are set as appropriate.
  • the hydrothermal reaction treatment conditions include a liquid temperature in the range of 250 to 450 ° C, reaction time Is preferably in the range of 1 second to 48 hours. If the reaction treatment temperature and time are equal to or higher than the lower limit value, crystallization is promoted, the optical property change is large and the transition temperature range is narrowed. And the change in optical characteristics can be maintained.
  • the transition temperature width of the vanadium dioxide-containing particles is measured as follows. First, an aqueous dispersion containing vanadium dioxide-containing particles is prepared and mixed in polyvinyl alcohol dissolved in water. This mixed solution is applied onto a PET film, applied with a wire bar so that the film thickness after drying becomes a predetermined thickness, and then dried to produce a measurement film. Using this measurement film, the temperature is changed in increments of 1 ° C. from 10 ° C. to 85 ° C., the light transmittance at a wavelength of 2000 nm at each temperature is measured, and the transition temperature width is calculated. Specifically, the lowest temperature at which the light transmittance difference becomes 1% or more with respect to the light transmittance measured at 10 ° C.
  • transition start temperature is the transition start temperature
  • the light transmittance difference with respect to the light transmittance measured at 85 ° C is the transition start temperature
  • 85 ° C. is used as the transition end temperature
  • the transition temperature width is calculated by the following formula.
  • Transition temperature range (° C) Transition end temperature-Transition start temperature
  • the transition temperature width of the vanadium dioxide-containing particles of the present invention is preferably in the range of 1 to 25 ° C.
  • the solid content concentration of vanadium dioxide derived from the vanadium-containing compound in the hydrothermal reaction is preferably within the range of 0.1 to 20% by mass.
  • the solid content concentration of vanadium dioxide is in the range of 0.1 to 20% by mass, crystal growth can be suppressed and dispersion stabilization can be achieved.
  • the hydrothermal reaction is performed with stirring because the particle diameter of the vanadium dioxide-containing particles can be made more uniform.
  • the hydrothermal reaction process may be implemented by a batch type and may be implemented by a continuous type.
  • thermochromic film of the present invention contains the vanadium dioxide-containing particles of the present invention described above.
  • thermochromic film of the present invention is a light at a wavelength of 1300 nm under conditions of 15 ° C. and 70 ° C. after 4000 cycles of cold heat treatment, with treatment at 0 ° C. for 15 minutes and treatment at 85 ° C. for 15 minutes as one cycle.
  • the transmittance difference is preferably maintained at a rate of 60% or more, and more preferably maintained at a rate of 80% or more with respect to the initial light transmittance difference (before the heat treatment).
  • the heat treatment is performed using a thermal shock apparatus TSA-303EL (manufactured by ESPEC Corporation).
  • thermochromic film of the present invention a film provided with a transparent substrate and an optical functional layer will be described as an example, but the present invention is not particularly limited thereto.
  • thermochromic film is preferably provided with a transparent substrate and an optical functional layer, and the optical functional layer preferably contains a resin and the vanadium dioxide-containing particles of the present invention described above.
  • the transparent base material applicable to the thermochromic film is not particularly limited as long as it is transparent, and examples thereof include glass, quartz, and a transparent resin film. However, flexibility and production suitability (roll to roll suitability) can be exemplified. From this point of view, 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, the curved surface of the glass when bonded to the glass substrate when making laminated glass The follow-up to is improved.
  • the transparent substrate preferably has a thermal shrinkage within a range of 0.1 to 3.0% at a temperature of 150 ° C. from the viewpoint of preventing wrinkles of the thermochromic film.
  • a range of 0% is more preferable, and a range of 1.9 to 2.7% is still more preferable.
  • the transparent substrate applicable to the thermochromic film is not particularly limited as long as it is transparent, and various transparent resin films can be used.
  • polyolefin films for example, polyethylene films, polypropylene films) Etc.
  • polyester film for example, polyethylene terephthalate film, polyethylene naphthalate film, etc.
  • polyvinyl chloride film for example, triacetyl cellulose film, etc., preferably polyester film, triacetyl cellulose film, more preferably It is a polyester film.
  • 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 when a laminated glass provided with a thermochromic film is used as an automobile windshield.
  • fine particles may be contained within a range that does not impair the transparency in order to facilitate handling.
  • the fine particles applicable to the transparent resin film include inorganic fine particles such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide.
  • organic fine particles such as crosslinked polymer fine particles and calcium oxalate.
  • Examples of the method of adding the fine particles include a method of adding fine particles into a resin (for example, polyester) as a raw material for forming the transparent resin film, a method of directly adding to the extruder, and the like. Either of these methods may be employed, or two methods may be used in combination.
  • various additives may be added to the transparent resin film as necessary. Examples of such additives include stabilizers, lubricants, crosslinking agents, anti-blocking agents, antioxidants, dyes, pigments, ultraviolet absorbers, and the like.
  • An optical functional layer containing the resin and the vanadium dioxide-containing particles of the present invention is provided on the transparent substrate.
  • the resin is not particularly limited, and a resin similar to that generally used for an optical functional layer of a thermochromic film (optical film) can be used, and preferably a water-soluble polymer can be used.
  • 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 vanadium dioxide-containing particles in the optical functional layer is preferably in the range of 1 to 60% by mass with respect to the total mass (100% by mass) of the optical functional layer from the viewpoint of obtaining desired thermochromic properties. More preferably, it is in the range of 5 to 50% by mass.
  • Various surfactants such as JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-219266.
  • Fluorescent brighteners sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate and other pH adjusters, antifoaming agents, diethylene glycol Lubricants, antiseptics, antifungal agents, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, thinning agents, lubricants, infrared absorbers, dyes And various known additives such as pigments.
  • the method for producing the thermochromic film (the method for forming the optical functional layer) is not particularly limited, and can be applied in the same manner as in a known method or appropriately modified except that the vanadium dioxide-containing particles of 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. 2761791.
  • ⁇ Dispersion> When the vanadium dioxide-containing particles of the present invention are dispersed in water, a dispersion containing vanadium dioxide-containing particles that exhibits excellent thermochromic properties can be provided. When a dispersion containing the vanadium dioxide-containing particles is applied, a thermochromic film or the like exhibiting excellent thermochromic properties can be provided.
  • the solvent to be dispersed only needs to contain water, and a known solvent such as an organic solvent can be used as long as the function of vanadium dioxide is not impaired.
  • thermochromic property of the aqueous dispersion containing VO 2 -containing particles can be measured by using, for example, a spectrophotometer V-670 (manufactured by JASCO Corporation), and the light transmittance at a wavelength of 2000 nm that is not affected by the absorption peak of water. It can be measured as a difference.
  • the addition amount (atom%) of the element A and the element B in an Example is a value with respect to vanadium (100 atom%) in a reaction liquid.
  • “%” is used, but “mass%” is indicated unless otherwise specified.
  • Dispersions 101 to 141 containing vanadium dioxide-containing particles were prepared as follows.
  • a 5% by mass aqueous solution of a reducing agent, hydrazine monohydrate (N 2 H 4 .H 2 O, manufactured by Wako Pure Chemical Industries, Ltd., special grade) is slowly added dropwise to the obtained sol, and the reaction has a pH of 4.5.
  • a liquid liquid temperature 25 ° C.
  • pure water was added to prepare a solid content of 2.5% by mass in terms of vanadium dioxide.
  • the prepared reaction liquid is put in a commercially available autoclave for hydrothermal reaction treatment (manufactured by Sanai Kagaku Co., Ltd., HU-50 type (SUS main body is equipped with a 50 mL capacity Teflon (registered trademark) inner cylinder)) 280
  • a dispersion 101 containing vanadium dioxide-containing particles was prepared by hydrothermal reaction at 6 ° C. and 6.43 MPa for 24 hours.
  • VOSO 4 vanadium oxide sulfate
  • This reaction liquid was put into an autoclave having an internal volume of 500 mL, and subjected to a hydrothermal reaction at 270 ° C. and 5.51 MPa for 15 hours to prepare a dispersion liquid 102 containing vanadium dioxide-containing particles.
  • dispersion 105 in addition to rhodium as an additive element, manganese (electronegativity: 1.55, standard oxidation-reduction potential (25 ° C.): ⁇ 1.18 V) (MnSO 4 ⁇ 7H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.)
  • dispersion liquid 106 selenium (electronegativity: 2.55) (SeO 2 , manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade) was added as an additive element to the dispersion liquid 106.
  • Dispersions 107 to 132 were prepared in the same manner as in the preparation of dispersion 102, except that the types and addition amounts of element A and element B were changed as shown in Table IV.
  • the compounds containing element A or element B used for the preparation of each dispersion are as follows.
  • Zinc ZnSO 4 , Wako Pure Chemical Industries, 95.0 +% Cadmium: CdSO 4 , Wako Pure Chemical Industries, 44% as Cd Cobalt: CoSO 4 , Wako Pure Chemical Industries, 99.0 +% (as cobalt (II) sulfate heptahydrate)
  • Nickel NiSO 4 , manufactured by Wako Pure Chemical Industries, 99.9 +% (as nickel (II) sulfate hexahydrate)
  • Silver AgNO 3 , Wako Pure Chemical Industries, 99.5 +% Copper: CuSO 4 , Wako Pure Chemical Industries, 99.5 +% Bismuth: Bi 2 O 3 , Wako Pure Chemical Industries, 98.0 +% Antimony: KSb (OH) 6 , manufactured by SIGMA-ALDRICH, 99.99% Molybdenum: (NH 4 ) 6 Mo 7 O 24 , Wako Pure Chemical Industries, 99.997% Ruthenium: RuCl 3 , Wako Pure Chemical Industries, 85.
  • a dispersion 133 was prepared in the same manner as in the preparation of the dispersion 103 except that the types and addition amounts of the elements A and B were changed as shown in Table IV.
  • a dispersion 134 containing vanadium dioxide-containing particles was prepared using the flow reactor 101 having the hydrothermal reaction section 116 shown in FIG. 1 according to the following method.
  • vanadium oxide sulfate (IV) (VOSO 4 ) was dissolved in ion exchange water (dissolved oxygen amount: 8.1 mg / L) to 300 mL in the raw material liquid container 105, and this liquid was stirred,
  • element A cadmium 5.00 atom% (CdSO 4 , manufactured by Wako Pure Chemical Industries, 44% as Cd) and as element B molybdenum 3.00 atom% ((NH 4 ) 6 Mo 7 O 24 , manufactured by Wako Pure Chemical Industries, Ltd.
  • the raw material liquid 1 containing vanadium oxide oxide (IV), element A, element B, and alkali is fed from the raw material liquid container 105 through the flow path 106 by the pump 107, and is heated by a heating medium 115 at 25 ° C. and 30 MPa.
  • the pressure was applied so that
  • the ion-exchanged water that is the raw material liquid 2 is fed from the raw material liquid container 102 through the flow path 103 by the pump 104, and heated and pressurized by the heating medium 113 at 440 ° C. under the condition of 30 MPa to obtain supercritical water.
  • the raw material liquid 1 containing vanadium oxide oxide (IV), element A, element B and alkali and the raw material liquid 2 which is supercritical water at the confluence MP are as follows:
  • Raw material liquid 2 1
  • the reaction solution 1 was prepared by mixing under the conditions of 4: 4 and fed to the hydrothermal reaction section 116.
  • the reaction liquid 1 was sent to the heating section piping 117 disposed in the heating medium 114.
  • the treatment time passedage time was 60 seconds under the conditions of 450 ° C. and 30 MPa, and vanadium dioxide-containing particles were formed.
  • the reaction liquid 1 was cooled in the cooling unit 108 to prepare a dispersion liquid 134 containing vanadium dioxide-containing particles.
  • dispersion 135 containing vanadium dioxide-containing particles was prepared in the same manner except that the treatment temperature and pressure in the hydrothermal reaction were changed to 250 ° C. and 3.98 MPa.
  • dispersion 136 A dispersion 129 containing vanadium dioxide-containing particles was prepared in the same manner as in the preparation of the dispersion 134, except that the treatment temperature in the hydrothermal reaction was changed to 480 ° C.
  • a dispersion liquid 137 containing vanadium dioxide-containing particles was prepared in the same manner except that the treatment temperature and pressure in the hydrothermal reaction were changed to 230 ° C. and 2.80 MPa in the preparation of the dispersion liquid 126.
  • dispersion 138 A dispersion 138 containing vanadium dioxide-containing particles was prepared in the same manner as in the preparation of the dispersion 126, except that the treatment time in the hydrothermal reaction was changed to 48 hours.
  • dispersion 139 containing vanadium dioxide-containing particles was similarly performed except that the treatment temperature and pressure in the hydrothermal reaction were changed to 270 ° C., 5.51 MPa, and the treatment time (passage time) was changed to 1 second.
  • the treatment temperature and pressure in the hydrothermal reaction were changed to 270 ° C., 5.51 MPa, and the treatment time (passage time) was changed to 1 second.
  • dispersion 140 containing vanadium dioxide-containing particles was prepared in the same manner except that the treatment time in the hydrothermal reaction was changed to 120 hours.
  • a dispersion containing vanadium dioxide-containing particles was prepared in the same manner as in the preparation of the dispersion 134 except that the treatment temperature and pressure in the hydrothermal reaction were changed to 270 ° C., 5.51 MPa, and the treatment time (passage time) was changed to 0.3 seconds.
  • a liquid 141 was prepared.
  • TC properties ⁇ Thermochromic properties (TC properties)>
  • Each of the prepared dispersions was prepared to 20 g of an aqueous dispersion containing 5% by mass of vanadium dioxide-containing particles, and mixed in 10 g of polyvinyl alcohol dissolved in 90 g of water. This mixed solution was applied onto a PET film, applied with a wire bar so that the thickness after drying was 20 ⁇ m, and then dried at 60 ° C. for 24 hours to prepare a measurement film.
  • grains in the film for a measurement was 1 mass%, and thickness was 20 micrometers.
  • the light transmittance was measured by attaching a temperature control unit (manufactured by JASCO Corporation) to a spectrophotometer V-670 (manufactured by JASCO Corporation).
  • the light transmittance difference after the cold heat treatment was determined to be acceptable when the ratio was 60% or more with respect to the initial light transmittance difference, and more preferably 80% or more.
  • the heat treatment was performed using a thermal shock apparatus TSA-303EL (manufactured by ESPEC Corporation).
  • the present invention can be particularly suitably used for providing a method for producing vanadium dioxide-containing particles, thermochromic film and vanadium dioxide-containing particles having excellent fastness to thermal expansion accompanying heating and cooling.

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PCT/JP2017/037169 2016-12-16 2017-10-13 二酸化バナジウム含有粒子、サーモクロミックフィルム及び二酸化バナジウム含有粒子の製造方法 WO2018110062A1 (ja)

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