WO2016158620A1 - Film optique - Google Patents

Film optique Download PDF

Info

Publication number
WO2016158620A1
WO2016158620A1 PCT/JP2016/059238 JP2016059238W WO2016158620A1 WO 2016158620 A1 WO2016158620 A1 WO 2016158620A1 JP 2016059238 W JP2016059238 W JP 2016059238W WO 2016158620 A1 WO2016158620 A1 WO 2016158620A1
Authority
WO
WIPO (PCT)
Prior art keywords
optical film
fine particles
pigment
vanadium dioxide
optical
Prior art date
Application number
PCT/JP2016/059238
Other languages
English (en)
Japanese (ja)
Inventor
博和 小山
Original Assignee
コニカミノルタ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to JP2017509849A priority Critical patent/JPWO2016158620A1/ja
Publication of WO2016158620A1 publication Critical patent/WO2016158620A1/fr

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters

Definitions

  • the present invention relates to an optical film, and more particularly to an optical film containing vanadium dioxide having thermochromic properties capable of adjusting the near-infrared shielding rate according to the environmental temperature.
  • the near-infrared light shielding film is preferably used due to its high near-infrared light shielding ability in a low-latitude zone near the equator where the illuminance of sunlight is high.
  • a method of applying a thermochromic material that controls the optical properties of near-infrared light shielding and transmission to the near-infrared light shielding film has been studied.
  • a typical example is vanadium dioxide (hereinafter also referred to as VO 2 ).
  • VO 2 is known to undergo a phase transition in a temperature region around 67 ° C. and exhibit thermochromic properties.
  • the optical film using the characteristics of VO 2 can shield near-infrared light that causes heat at a high temperature, and can exhibit characteristics that transmit near-infrared light at a low temperature. This makes it possible to block near-infrared light when the summer is hot and suppress the temperature rise in the room, and to capture light energy when the winter is cold.
  • VO 2 vanadium dioxide
  • a method of obtaining vanadium dioxide (VO 2 ) nanoparticles by hydrothermal synthesis from a vanadium compound and hydrazine or a hydrate thereof is disclosed (for example, see Patent Document 1).
  • a thermochromic film by dispersing VO 2 nanoparticles prepared by the hydrothermal synthesis method in a transparent resin to form a VO 2 dispersed resin layer on a transparent substrate.
  • a possible method is disclosed (for example, see Patent Document 2).
  • thermochromic effect is reduced because the large change width of the shielding ratio and transmittance of near-infrared light before and after the transition is reduced. was there.
  • the temperature is relatively low, for example, in the early spring of Japan, there is a problem that the heat shielding property does not appear when the solar radiation is strong.
  • the present invention has been made in view of the above-mentioned problems, and the problem is that in an optical film containing vanadium dioxide capable of adjusting the near-infrared light shielding rate according to the environmental temperature, the near red before and after the transition of vanadium dioxide. It can control the transition without losing the large change in the shielding ratio and transmittance of outside light, and can fully exert the effect of thermodynamics. It is providing the optical film which can express.
  • the present inventor contains vanadium dioxide fine particles having thermochromic properties and a dye or pigment that absorbs light within a specific wavelength range, and the light wavelength range is within the range.
  • the transition can be controlled without losing the change range of the shielding effect and transmission effect of near-infrared light before and after the transition of vanadium dioxide.
  • the present inventors have found that the thermochromic effect can be sufficiently exerted, and that the heat shielding property can be expressed when the tingling feeling is strong even at a low temperature, and the present invention has been achieved.
  • An optical film containing vanadium dioxide fine particles having thermochromic properties Contains a dye or pigment that absorbs light in the light wavelength range of 650-700 nm, and An optical film characterized in that an average optical absorptance of the optical film within the light wavelength range is within a range of 30 to 85% at 23 ° C.
  • Item 1 or Item 2 is characterized in that the dye or pigment that absorbs light within the light wavelength range of 650 to 700 nm is a pigment having a maximum absorption wavelength within the light wavelength range of 600 to 750 nm.
  • the dye or pigment that absorbs light within the light wavelength range of 650 to 700 nm is a pigment having a maximum absorption wavelength within the light wavelength range of 600 to 750 nm.
  • Optical film is characterized in that the dye or pigment that absorbs light within the light wavelength range of 650 to 700 nm is a pigment having a maximum absorption wavelength within the light wavelength range of 600 to 750 nm.
  • the dye or pigment that absorbs light in the light wavelength range of 650 to 700 nm is contained in the same layer as the layer containing the vanadium dioxide fine particles or in an adjacent layer in direct contact with the layer containing the vanadium dioxide fine particles.
  • the average optical absorptance of the optical film within a light wavelength range of 650 to 700 nm is within a range of 50 to 70% at 23 ° C.
  • Item 10 The optical film according to any one of Items 1 to 9, wherein a spectral transmittance of the optical film at a light wavelength of 550 nm is within a range of 30 to 60% at 23 ° C.
  • the transition can be controlled and the effect of thermochromic properties can be sufficiently exhibited without losing the large change width of the near-infrared light shielding rate and transmittance before and after the transition of vanadium dioxide.
  • the expression mechanism / action mechanism that has achieved the above-described object effect of the present invention is not clear, but is presumed as follows.
  • the optical film of the present invention contains thermochromic vanadium dioxide fine particles and a dye or pigment that absorbs light in the light wavelength range of 650 to 700 nm, and thus efficiently absorbs solar heat absorbed by the dye or pigment.
  • the optical film of the present invention has an average light absorptance in the range of 30 to 85% at a light wavelength of 650 to 700 nm at 23 ° C., so that the optical film efficiently absorbs solar heat, and optical The temperature of the optical film rises before the environmental temperature where the film is placed.
  • the ambient temperature is somewhat lower without doping the vanadium dioxide fine particles with a metal such as tungsten (W) or molybdenum (Mo) to lower the transition temperature and lower the thermochromic properties.
  • W tungsten
  • Mo molybdenum
  • thermochromic properties appear when the sun is strong, and it shields sunlight.
  • the transition temperature can be controlled so that the effect of thermochromic properties can be sufficiently exerted, and when the temperature is low, the thermal barrier property can be expressed when the sensation is strong.
  • Schematic sectional view showing an example of the basic configuration of the optical film of the present invention Schematic sectional view showing another example of the basic configuration of the optical film of the present invention
  • Schematic sectional view showing another example of the basic configuration of the optical film of the present invention Schematic sectional view showing another example of the basic configuration of the optical film of the present invention
  • the optical film of the present invention is an optical film containing thermochromic vanadium dioxide fine particles, contains a dye or a pigment that absorbs light in the light wavelength range of 650 to 700 nm, and is in the light wavelength range.
  • the average optical absorptance of the optical film is in the range of 30 to 85% at 23 ° C.
  • the dye or pigment that absorbs light within the light wavelength range of 650 to 700 nm is within the light wavelength range of 600 to 750 nm from the viewpoint of more manifesting the intended effect of the present invention.
  • a dye or pigment having a maximum absorption wavelength is preferred. As a result, light within the light wavelength range of 650 to 700 nm can be efficiently absorbed.
  • the dye or pigment that absorbs light in the light wavelength range of 650 to 700 nm is preferably a pigment having a maximum absorption wavelength in the light wavelength range of 600 to 750 nm. That is, the dye system absorbs the absorbed energy immediately and reaches a uniform temperature, whereas the pigment system increases the temperature as particles, and the temperature near the particles can be increased. Is preferable.
  • the pigment having the maximum absorption wavelength in the light wavelength range of 600 to 750 nm is preferably a metal phthalocyanine pigment from the viewpoint of the high extinction coefficient and weather resistance.
  • the number average primary particle size of the pigment particles constituting the pigment is smaller than the number average primary particle size of the vanadium dioxide fine particles, the balance of heat absorption and release of the pigment particles and vanadium dioxide fine particles, This is preferable in that the solar heat absorbed by the particles can be efficiently transferred to the vanadium dioxide fine particles.
  • the dye or pigment that absorbs light in the light wavelength range of 650 to 700 nm is in the same layer as the layer containing the vanadium dioxide fine particles, or an adjacent layer in direct contact with the layer containing the vanadium dioxide fine particles. It is preferable that it is contained because the solar heat absorbed by the dye or pigment can be efficiently transferred to the vanadium dioxide fine particles.
  • the change width of the shielding effect and the transmission effect before and after the transition of the vanadium dioxide fine particles is increased, and the effect of thermochromic properties is increased. It is preferable in that it can be performed.
  • the spectral transmittance of the optical film at a light wavelength of 1300 nm is 50% or more at 23 ° C. because the shielding effect and the transmission effect before and after the transition of the vanadium dioxide fine particles can be effectively used.
  • the spectral transmittance of the optical film at a light wavelength of 1300 nm is preferably 40% or less at 70 ° C.
  • the optical film when the average optical absorptance of the optical film in the light wavelength range of 650 to 700 nm is in the range of 50 to 70% at 23 ° C., the optical film absorbs solar heat more efficiently, and the solar radiation. When it is strong, chromic properties are exhibited, which is preferable in terms of sunlight shielding properties.
  • the spectral transmittance of the optical film at a light wavelength of 550 nm is preferably in the range of 30 to 60% at 23 ° C. from the viewpoint of coloring of the optical film.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the optical film of the present invention is an optical film containing vanadium dioxide fine particles having thermochromic properties, and is a dye or pigment that absorbs light within a light wavelength range of 650 to 700 nm (hereinafter, simply “dye or pigment”, Or an average light absorptance of the optical film within the light wavelength range within a range of 30 to 85% at 23 ° C.
  • the measurement of an average spectral transmittance and an average spectral reflectance can be measured using a spectrophotometer. In the present invention, measurement was performed using an ultraviolet-visible near-infrared spectrophotometer V-670 manufactured by JASCO Corporation. After setting the temperature in the temperature-controlled room to 23 ° C. and the humidity 55RH so that the temperature of the film would be 23 ° C., the measurement sample (optical film) was left in the temperature-controlled room for 3 hours to be in an equilibrium state. The above measurements were made.
  • the average light absorptance within the light wavelength range of 650 to 700 nm is more preferably within a range of 50 to 70% at 23 ° C., from the viewpoint of more efficiently absorbing solar heat.
  • the spectral transmittance at a light wavelength of 1300 nm is 50% or more at 23 ° C. because the shielding effect and the transmission effect before and after the transition of the vanadium dioxide fine particles can be effectively used.
  • the spectral transmittance at a light wavelength of 550 nm is preferably in the range of 30 to 60% at 23 ° C. from the viewpoint of coloring of the optical film.
  • the measurement of these spectral transmittances can also use the same spectrophotometer as the above.
  • the coating amount of the coating solution containing the dye or pigment can be controlled.
  • the coating amount varies depending on the absorption coefficient of the dye or pigment, but is approximately in the range of 0.01 to 1 g as the coating amount per 1 m 2 of the dye or pigment.
  • the dye or pigment that absorbs light in the light wavelength range of 650 to 700 nm in the present invention is not particularly limited as long as it is a material that absorbs light in the range of 650 to 700 nm, but has maximum absorption in the range of 600 to 750 nm.
  • a dye or pigment having a wavelength is more preferable because it can efficiently absorb light in the range of 650 to 700 nm.
  • the “dye” refers to a dye that is used as a coloring material to be colored and is dissolved in any solvent such as water or an organic solvent.
  • “Pigment” refers to a pigment that is used as a coloring material to be colored and is in the form of a fine powder of a pigment that does not dissolve in water or an organic solvent.
  • anthraquinone dyes include anthraquinone dyes, phthalocyanine dyes, triphenylmethane dyes, triarylmethane dyes, and indigo dyes.
  • Anthraquinone dyes include, for example, C.I. I. Solvent Blue 35 (maximum absorption wavelength 623, 670 nm), C.I. I. Solvent Blue 36 (maximum absorption wavelength 643 nm), C.I. I. Solvent Blue 59 (maximum absorption wavelength 645 nm), C.I. I. Solvent Blue 63 (maximum absorption wavelength 645 nm), C.I.
  • pigments compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. ) Can be listed.
  • Pigment blue 15: 3 (maximum absorption wavelength 630, 720 nm), C.I. I. Pigment Blue 15: 4 (maximum absorption wavelength 640, 740 nm), C.I. I. Pigment Blue 16 (maximum absorption wavelength 620, 690 nm) or the like can be preferably used.
  • a pigment rather than the above-mentioned dye.
  • a metal phthalocyanine pigment is more preferable in view of the high extinction coefficient and weather resistance.
  • the mechanism by which pigment systems are preferred over dye systems is not clearly understood, but dye systems quickly diffuse the absorbed energy to a uniform temperature, while pigment systems have a temperature as particles. It is preferable in that it rises and the vicinity of the particles can be heated to a higher temperature.
  • the optical film is colored green. It is more preferable to use a pigment in combination so that the spectral transmittance at a light wavelength of 550 nm at a film temperature of 23 ° C. is 30 to 60%, which is close to gray.
  • the green pigment include C.I. I. Pigment green 36, C.I. I. A green pigment containing a compound in which the central metal in Pigment Green 36 is a metal other than Cu, such as Zn; I. Pigment green 7, C.I. I. Pigment red 122, C.I. I. And CI Pigment Red 254.
  • the optical film of the present invention is characterized in that any layer constituting the optical film contains thermochromic vanadium dioxide fine particles and the dye or pigment.
  • the layer containing the vanadium dioxide fine particles having thermochromic properties and the layer containing the dye or pigment may be the same layer or different layers, but contain the dye or pigment.
  • the layer is preferably the same layer as the layer containing vanadium dioxide fine particles or an adjacent layer in direct contact with the layer containing vanadium dioxide fine particles. This is because the solar heat absorbed by the dye or pigment can be efficiently transferred to the vanadium dioxide fine particles.
  • Typical configurations of the optical film of the present invention include the following configurations (1) to (7), but are not limited thereto.
  • Colorant layer / hard coat layer containing the dye or pigment / transparent substrate / optical functional layer containing the vanadium dioxide fine particles / adhesive layer see FIG. 1A
  • Hard coat layer / transparent substrate / optical functional layer containing the vanadium dioxide fine particles / colorant layer / adhesive layer containing the dye or pigment see FIG. 1B
  • Hard coat layer / transparent substrate / optical functional layer containing the vanadium dioxide fine particles / colorant layer / adhesive layer containing the dye or pigment see FIG.
  • Hard coat layer / transparent substrate / colorant layer / optical functional layer / adhesive layer containing the vanadium dioxide fine particles and the dye or pigment see FIG. 1D
  • Hard coat layer / Optical functional layer / transparent substrate containing vanadium dioxide fine particles / Colorant layer / adhesive layer containing the dye or pigment see FIG. 1E
  • Colorant layer / hard coat layer containing the dye or pigment / Optical functional layer / transparent substrate / adhesive layer containing the vanadium dioxide fine particles see FIG. 1F
  • Hard coat layer / colorant layer containing the vanadium dioxide fine particles and the dye or pigment, and optical functional layer / transparent substrate / adhesive layer see FIG. 1G
  • the adhesive layer can be attached to glass (for example, glass 7 shown in FIGS. 1A to 1G). The configurations (1) to (7) will be described below.
  • the optical functional layer 3 containing the vanadium dioxide fine particles having thermochromic properties and the adhesive layer 5 are laminated in this order on one surface of the transparent substrate 2.
  • a hard coat layer 4a containing a dye or pigment that absorbs light in the light wavelength range of 650 to 700 nm is laminated.
  • the optical function layer 3 is present in a state where vanadium dioxide fine particles are dispersed in a binder resin.
  • the dye or pigment is present in a dispersed state.
  • the number average particle diameter of primary particles of vanadium dioxide in the optical functional layer 3 is preferably larger than the number average particle diameter of primary particles of pigment particles constituting the pigment.
  • the average particle size of the vanadium dioxide fine particles in the optical functional layer can be determined according to the following method.
  • the side surface of the optical functional layer 3 constituting the optical film 1 is trimmed with a microtome to produce an ultrathin section having a cross section as shown in FIG. 1A.
  • the ultrathin section is photographed at 10,000 to 100,000 times using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the particle diameter of the primary particles of vanadium dioxide fine particles present as single particles existing in a certain region of the photographed cross section is measured.
  • the number of vanadium dioxide fine particles to be measured is preferably in the range of 50 to 100. If it is not spherical, the projected area of the particle is converted into a circle, and its diameter is taken as the particle size. For each primary particle diameter, the number average diameter is determined.
  • the cut-out cross-sectional portion has a variation in particle distribution, such measurement is performed for 10 different cross-sectional regions, the whole number-average diameter is obtained, and this is the number-average particle size (nm) referred to in the present invention. It was.
  • the primary particle diameter is preferably in the range of 5 to 100 nm.
  • the primary particle size of the pigment particles constituting the pigment is preferably in the range of 1 to 100 nm.
  • the average particle diameter of the pigment particles can be determined, for example, by observing an ultrathin section with a transmission electron microscope in the same manner as the primary particle diameter of the vanadium dioxide fine particles.
  • the dye or pigment is contained in the adhesive layer 5b which is an adjacent layer in direct contact with the optical functional layer 3 containing vanadium dioxide fine particles.
  • the dye or pigment is contained in the colorant layer 6 that is an adjacent layer in direct contact with the optical functional layer 3 containing vanadium dioxide fine particles, and on the colorant layer 6. Further, an adhesive layer 5 is formed.
  • the dye or pigment is contained in the same layer as the optical functional layer 3d containing vanadium dioxide fine particles. In the optical film 1 shown in FIG.
  • the dye or pigment is contained in the colorant layer 6 which is an adjacent layer in direct contact with the optical functional layer 3 and the transparent substrate 2 containing vanadium dioxide fine particles.
  • An adhesive layer 5 is further formed on the agent layer.
  • This optical film has a hybrid structure in which the transparent substrate 2 also serves as the optical functional layer 3.
  • the dye or pigment is contained in the hard coat layer 4f that directly contacts the optical functional layer 3 and the transparent substrate 2 containing vanadium dioxide fine particles.
  • This optical film has a hybrid structure in which the transparent substrate 2 also serves as the optical functional layer 3.
  • 1G is a case where the dye or pigment is contained in the same layer as the optical functional layer 3g and the transparent base material 2g containing vanadium dioxide fine particles.
  • This optical film 1 is also a transparent base material.
  • 2 g is a hybrid structure that also serves as the optical functional layer 3 g.
  • vanadium dioxide fine particles are dispersed in the binder resin, similarly to the optical functional layer 3 shown in FIG. 1A.
  • the hard coat layer 4 shown in FIGS. 1B to 1E and FIG. 1G contains no dye or pigment.
  • the optical functional layer 3 / transparent substrate 2 shown in FIGS. 1E and 1F and the optical functional layer 3g / transparent substrate 2g shown in FIG. 1G are contained in the transparent substrate 2 or the polymer constituting the transparent substrate 2g.
  • vanadium dioxide fine particles are present in a dispersed state.
  • optical functional layer which is a constituent element of the optical film of the present invention, a transparent substrate provided as necessary, a colorant layer, an adhesive layer, a hard coat layer, and a near-infrared light shielding layer will be described.
  • the optical functional layer according to the present invention contains vanadium dioxide fine particles and a binder resin.
  • the same layer as the optical functional layer containing the vanadium dioxide fine particles may contain a dye or pigment that absorbs light in the light wavelength range of 650 to 700 nm, or the different layer may include the dye or pigment. It may contain dyes or pigments.
  • the binder resin an aqueous binder resin or a hydrophobic binder resin can be used as will be described later.
  • an optical functional layer forming coating liquid is prepared by mixing an aqueous binder resin solution prepared by dissolving an aqueous binder resin in an aqueous solvent in the state of the dispersion liquid, and this optical functional layer forming coating liquid.
  • a method of forming an optical functional layer by coating and drying on a transparent substrate by a wet coating method is preferred.
  • vanadium dioxide fine particles are prepared by a solvent substitution step without preparing a drying step after preparing vanadium dioxide fine particles by an aqueous synthesis method. After preparing the solvent dispersion, mix and dissolve with a hydrophobic binder resin, etc. to prepare a non-aqueous optical functional layer-forming coating solution.
  • This non-aqueous optical functional layer-forming coating solution is prepared by a wet coating method. A method of forming an optical functional layer by coating and drying on a transparent substrate is preferred.
  • the vanadium dioxide fine particles and the binder resin will be described in order.
  • the crystal form of the vanadium dioxide fine particles according to the present invention is not particularly limited, but rutile vanadium dioxide fine particles (VO 2 fine particles) may be used from the viewpoint of efficiently expressing thermochromic properties (automatic light control). Is particularly preferred.
  • the vanadium dioxide fine particles according to the present invention may contain VO 2 fine particles of other crystal type such as A-type or B-type within a range that does not impair the purpose.
  • the metal component of the vanadium dioxide fine particles is vanadium, and thereby, good thermochromic properties can be exhibited. That is, when a metal other than vanadium is doped, it is sufficient if it is doped with less than 0.5 atomic%.
  • vanadium for example, tungsten (W), molybdenum (Mo), niobium (Nb), tantalum (Ta), tin (Sn), rhenium (Re), iridium (Ir), osmium (Os), ruthenium ( At least one element selected from the group consisting of Ru), germanium (Ge), chromium (Cr), iron (Fe), gallium (Ga), aluminum (Al), fluorine (F) and phosphorus (P). It may be included.
  • the aspect ratio of the vanadium dioxide fine particles is preferably in the range of 1.0 to 3.0.
  • the vanadium dioxide fine particles having such characteristics have a sufficiently small aspect ratio and an isotropic shape, the dispersibility when added to a solution is good.
  • the single crystal since the single crystal has a sufficiently small particle size, it can exhibit better thermochromic properties than conventional fine particles.
  • the concentration of the vanadium dioxide fine particles in the optical functional layer according to the present invention is not particularly limited, but is generally preferably in the range of 5 to 60% by mass, more preferably, based on the total mass of the optical functional layer. It is within the range of 5 to 40% by mass, and more preferably within the range of 5 to 30% by mass.
  • a method for producing vanadium dioxide fine particles includes a method of pulverizing a VO 2 sintered body synthesized by a solid phase method, and a vanadium compound such as divanadium pentoxide (V 2 O 5 ) or ammonium vanadate as a raw material.
  • a vanadium compound such as divanadium pentoxide (V 2 O 5 ) or ammonium vanadate as a raw material.
  • An aqueous synthesis method in which particles are grown while synthesizing VO 2 in the liquid phase can be mentioned.
  • the method for producing the vanadium dioxide fine particles according to the present invention is a method in which vanadium dioxide fine particles are synthesized using a vanadium compound as a raw material while synthesizing vanadium dioxide fine particles in a liquid phase in that the average primary particle size is small and variation in particle size can be suppressed.
  • a growing aqueous synthesis method is preferred.
  • examples of the aqueous synthesis method include a hydrothermal synthesis method and an aqueous synthesis method using a supercritical state. Details of the hydrothermal synthesis method will be described later. The details of the water-based synthesis method using the supercritical state (also referred to as supercritical hydrothermal synthesis method) are disclosed in, for example, paragraph numbers (0011) and (0015) to (0018) of JP-A-2010-58984. ) Can be referred to.
  • aqueous synthesis methods it is preferable to apply the hydrothermal synthesis method.
  • a method for producing vanadium dioxide fine particles if necessary, fine TiO 2 fine particles that become the core of particle growth are added as core particles, and vanadium dioxide fine particles are produced by growing the core particles. You can also.
  • a substance (I) containing vanadium (V), hydrazine (N 2 H 4 ) or a hydrate thereof (N 2 H 4 .nH 2 O), and water are mixed to prepare a solution (A).
  • This solution may be an aqueous solution in which the substance (I) is dissolved in water, or a suspension in which the substance (I) is dispersed in water.
  • the substance (I) examples include divanadium pentoxide (V 2 O 5 ), ammonium vanadate (NH 4 VO 3 ), vanadium trichloride (VOCl 3 ), sodium metavanadate (NaVO 3 ), and the like. .
  • the substance (I) is not particularly limited as long as it is a compound containing pentavalent vanadium (V). Hydrazine (N 2 H 4 ) and its hydrate (N 2 H 4 .nH 2 O) function as a reducing agent for the substance (I) and have a property of being easily dissolved in water.
  • the solution (A) may further contain a substance (II) containing an element to be added in order to add an element to the finally obtained vanadium dioxide (VO 2 ) single crystal fine particles.
  • the element to be added include tungsten (W), molybdenum (Mo), niobium (Nb), tantalum (Ta), tin (Sn), rhenium (Re), iridium (Ir), osmium (Os), ruthenium ( Ru), germanium (Ge), chromium (Cr), iron (Fe), gallium (Ga), aluminum (Al), fluorine (F), or phosphorus (P).
  • this solution (A) may further contain a substance (III) having oxidizing property or reducing property.
  • the substance (III) include hydrogen peroxide (H 2 O 2 ).
  • hydrothermal reaction treatment is performed using the prepared solution (A).
  • “hydrothermal reaction” means a chemical reaction that occurs in hot water (subcritical water) whose temperature and pressure are lower than the critical point of water (374 ° C., 22 MPa).
  • the hydrothermal reaction treatment is performed, for example, in an autoclave apparatus.
  • Single crystal fine particles containing vanadium dioxide (VO 2 ) are obtained by the hydrothermal reaction treatment.
  • the conditions of the hydrothermal reaction treatment are set as appropriate, but the temperature of the hydrothermal reaction treatment is, for example, within the range of 250 to 350 ° C. Preferably, it is in the range of 250 to 300 ° C, more preferably in the range of 250 to 280 ° C.
  • the hydrothermal reaction treatment time is preferably in the range of 1 hour to 5 days, for example. Increasing the time can control the particle size and the like of the obtained single crystal fine particles, but an excessively long processing time increases the energy consumption.
  • the surface of the obtained vanadium dioxide fine particles may be subjected to a coating treatment or a surface modification treatment with a resin. Thereby, the surface of vanadium dioxide fine particles is protected, and surface-modified single crystal fine particles can be obtained.
  • the surface of the vanadium dioxide fine particles is coated with the same or the same kind of resin as the aqueous binder resin.
  • the “coating” as used in the present invention is a state in which the entire surface of the particle is completely covered with the resin with respect to the vanadium dioxide fine particles, or a part of the particle surface is covered with the resin. It may be in a state.
  • thermochromic vanadium dioxide VO 2
  • the dispersion of vanadium dioxide fine particles prepared by the above-mentioned aqueous synthesis method contains impurities such as residues generated in the synthesis process, and triggers the generation of secondary agglomerated particles when forming the optical functional layer. Thus, it may become a deterioration factor in long-term storage of the optical functional layer, and it is preferable to remove impurities in advance at the stage of the dispersion.
  • the vanadium dioxide fine particle dispersion As a method for removing impurities in the vanadium dioxide fine particle dispersion, a conventionally known means for separating foreign substances and impurities can be applied.
  • the vanadium dioxide fine particle dispersion is centrifuged to precipitate the vanadium dioxide fine particles. It is possible to remove impurities in the supernatant and add and disperse the dispersion medium again, or to remove impurities out of the system using an exchange membrane such as an ultrafiltration membrane. From the viewpoint of preventing aggregation, the method using an ultrafiltration membrane is most preferable.
  • Examples of the material for the ultrafiltration membrane include cellulose, polyethersulfone, and polytetrafluoroethylene (abbreviation: PTFE). Among these, polyethersulfone and PTFE are preferably used.
  • the solvent replacement step is composed of a concentration step of concentrating the dispersion containing vanadium dioxide fine particles and a solvent dilution step of adding and diluting the solvent to the concentrate, and includes a concentration step and a subsequent solvent dilution step.
  • the treatment operation is preferably repeated twice or more to prepare a non-aqueous solvent dispersion containing vanadium dioxide fine particles.
  • concentration means used in the step of concentrating the specific dispersion containing vanadium dioxide fine particles an ultrafiltration method is preferable.
  • the solvent applicable in the solvent replacement treatment according to the present invention is an organic solvent, preferably a non-aqueous organic solvent.
  • it is a step of preparing a solvent dispersion containing vanadium dioxide fine particles by replacing water, which is a medium constituting the aqueous dispersion containing vanadium oxide-containing fine particles, with an organic solvent.
  • the solvent is not particularly limited and can be appropriately selected.
  • ketone solvents such as acetone, dimethyl ketone and methyl ethyl ketone
  • alcohol solvents such as methanol, ethanol and isopropyl alcohol
  • chlorine solvents such as chloroform and methylene chloride.
  • Solvents aromatic solvents such as benzene and toluene, ester solvents such as methyl acetate, ethyl acetate and butyl acetate, glycol ether solvents such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether, dioxane, hexane, octane, diethyl ether, Any material that dissolves the hydrophobic binder resin to be applied at the same time, such as dimethylformamide, can be used.
  • FIG. 2 is a schematic flow diagram showing an example of a solvent replacement processing apparatus applicable to the present invention.
  • the solvent replacement processing apparatus 10 shown in FIG. 2 adjusts the preparation tank 11 for storing the dispersion liquid 12 containing the vanadium dioxide fine particles prepared above, the solvent stock tank 17 for storing the solvent 18 for dilution, and the solvent 18.
  • An ultrafiltration unit 15 is disposed as a concentrating means in the route of the circulation line 13 for circulating the solvent supply line 19 to be added to the pot 11 and the preparation tank 11 by the circulation pump 14.
  • Step (A) The dispersion liquid containing the vanadium dioxide fine particles prepared by the above method is stored as the dispersion liquid 12 in the preparation kettle 11 and is circulated by the circulation pump 14. Water is discharged from the discharge port 16 and concentrated to a predetermined concentration. As a standard of concentration, it concentrates to 20 volume% with respect to the initial volume. It is preferable to avoid excessive concentration beyond this because particle aggregation occurs as the particle density increases. In this concentration operation, it is important not to dry the dispersion.
  • Step (B) Next, 80% by mass of the solvent 18 is added from the solvent stock kettle 17 via the solvent supply line 19 to the dispersion 12 concentrated to 20% by volume, and sufficiently stirred and mixed. A primary solvent-substituted dispersion 12 is prepared.
  • Step (C) Next, in the same manner as in the above step (A), the medium (water + solvent) in the dispersion is discharged 16 outside the system by the ultrafiltration unit 15 while being circulated by the circulation pump 14. Concentrate again to a concentration of 20% by volume.
  • Step (D) Next, in the same manner as in the above step (B), 80% by mass of the solvent 18 is added from the solvent stock kettle 17 via the solvent supply line 19 to the concentrated dispersion, and the mixture is sufficiently stirred. Mixing is performed to prepare the first solvent-substituted dispersion liquid 12.
  • Step (E) Finally, the concentration and solvent dilution operations in Step (A) and Step (B) are repeated at least twice, so that the water content is within the range of 0.1 to 5.0% by mass.
  • a solvent dispersion containing the adjusted vanadium dioxide fine particles is prepared.
  • the water content can be determined by measuring, for example, by the Karl Fischer method.
  • the solvent dispersion liquid containing vanadium dioxide fine particles according to the present invention can contain water to some extent, and is 30% by mass or less, preferably 10% by mass or less, and particularly preferably 5.0% by mass. It is as follows. Moreover, a minimum is 0.01 mass% or more, Preferably it is 0.05 mass% or more, Most preferably, it is 0.1 mass%. Accordingly, the water content is preferably in the range of 0.01 to 30% by mass, and in the range of 0.1 to 5.0% by mass is a particularly preferable embodiment.
  • the film forming property of the coexisting hydrophobic binder can be prevented at the time of forming the optical functional layer, and the haze can be reduced to 0.01% by mass. % Or more, the change width between the infrared transmittance and the infrared shielding rate at the time of temperature change can be increased to some extent. In particular, when the water content is 5.0% by mass or less, it is possible to further suppress the effect of the oxidation of the vanadium dioxide fine particles and the film forming property of the coexisting hydrophobic binder, and to maintain the haze at a lower level. be able to. Moreover, by setting it as 0.1 mass% or more, the change width of the infrared rays transmittance
  • Vivaflow 50 (effective filtration area 50 cm 2 , fractional molecular weight 5000) manufactured by Sartorius steady is used as a filtration membrane, and ultrafiltration is performed at a flow rate of 300 ml / min (minutes), a hydraulic pressure of 100 kPa, and room temperature.
  • ultrafiltration device having a filtration membrane made of polyethersulfone and a molecular weight cut off of 300,000 (Pericon 2 cassette, manufactured by Nihon Millipore Corporation).
  • the binder resin applicable to the present invention is not particularly limited, but is preferably an aqueous binder resin or a hydrophobic binder resin.
  • a hydrophobic binder resin should be used when preparing a solvent dispersion containing vanadium dioxide fine particles by the solvent replacement step. It is preferable to use an aqueous binder resin when the solvent replacement step is not performed.
  • the aqueous binder resin referred to in the present invention represents a resin material that dissolves 0.5 g or more with respect to 100 g of water at 20 ° C., more preferably 1.0 g or more. Moreover, after making it melt
  • Dextrin dextran, saccharide derivatives such as dextran sulfate, naturally-derived materials such as thickening polysaccharides, polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylic Acrylic resins such as nitrile copolymer, vinyl acetate-acrylic acid ester copolymer, or acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid Acid-acrylic acid S Copolymer, styrene- ⁇ -methylstyrene-acrylic acid copolymer, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene acrylic resin, styrene-sodium
  • a polymer containing 50 mol% or more of repeating unit components having a hydroxy group which has a high affinity with vanadium dioxide fine particles and has a high effect of preventing particle aggregation even during drying of film formation, is preferable.
  • examples thereof include celluloses, polyvinyl alcohols, acrylic resins having a hydroxy group, etc.
  • polyvinyl alcohols and celluloses can be most preferably used.
  • Polyvinyl alcohols As the polyvinyl alcohol preferably used in the present invention, ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate can be used.
  • modified polyvinyl alcohol such as polyvinyl alcohol whose end is cation-modified or anion-modified polyvinyl alcohol having an anionic group is also included.
  • Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups as described in JP-A No. 61-10383.
  • Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride.
  • the ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.
  • Anion-modified polyvinyl alcohol is described in, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681 and JP-A-63-307979.
  • examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and a modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.
  • Nonionic modified polyvinyl alcohol includes, for example, a polyvinyl alcohol derivative in which a polyalkylene oxide group is added to a part of vinyl alcohol as described in JP-A-7-9758, and JP-A-8-25795.
  • the block copolymer of the vinyl compound and vinyl alcohol which have the described hydrophobic group is mentioned.
  • Polyvinyl alcohol can be used in combination of two or more different degrees of polymerization and different types of modification.
  • polyvinyl alcohol used in the present invention a synthetic product or a commercially available product may be used.
  • commercially available products used as polyvinyl alcohol include, for example, PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA-203, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-235 (above, manufactured by Kuraray Co., Ltd.), JC-25, JC-33, JF-03, JF-04, JF-05, JP- 03, JP-04, JP-05, JP-45 (above, manufactured by Nippon Vinegar Poval Co., Ltd.) and the like.
  • a water-soluble cellulose derivative is preferable, for example, carboxymethylcellulose (cellulose carboxymethyl ether), methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, Examples thereof include water-soluble cellulose derivatives such as hydroxypropylmethylcellulose, carboxymethylcellulose (cellulose carboxymethyl ether) and carboxyethylcellulose which are carboxylic acid group-containing celluloses.
  • Other examples include cellulose derivatives such as nitrocellulose, cellulose acetate propionate, cellulose acetate, and cellulose sulfate.
  • the water-based binder resin is a polymer containing 50 mol% or more of repeating units having a hydroxy group.
  • the repeating unit component is originally composed of three types. It has a hydroxy group, and some of these three hydroxy groups are substituted.
  • the content of 50 mol% or more of repeating unit components having a hydroxy group means that 50 mol% or more of the repeating unit component having a hydroxy group in this substituent or the repeating unit component in which one or more unsubstituted hydroxy groups remain is contained. Represents that.
  • gelatin As the gelatin applicable to the present invention, various gelatins that have been widely used in the field of silver halide photographic light-sensitive materials can be applied. For example, in addition to acid-processed gelatin and alkali-processed gelatin, production of gelatin is possible. Enzyme-treated gelatin and gelatin derivatives that undergo enzyme treatment in the process, that is, modified with a reagent that has an amino group, an imino group, a hydroxy group, or a carboxy group as functional groups in the molecule and has groups obtained by reaction with them. It may be quality. Well-known methods for producing gelatin are well known. H. James: The Theory of Photographic Process 4th. ed.
  • a gelatin hardener can be added as necessary.
  • known compounds that are used as hardeners for ordinary photographic emulsion layers can be used.
  • the thickening polysaccharide that can be used in the present invention is not particularly limited, and examples thereof include generally known natural simple polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides. The details of these polysaccharides can be referred to “Biochemical Encyclopedia (2nd edition), Tokyo Chemical Doujinshi”, “Food Industry”, Vol. 31 (1988), p.
  • the thickening polysaccharide referred to in the present invention is a polymer of saccharides and has a number of hydrogen bonding groups in the molecule. Due to the difference in hydrogen bonding strength between molecules depending on the temperature, the viscosity at low temperature and the viscosity at high temperature. It is a polysaccharide with a large difference in characteristics, and when adding metal oxide fine particles, it causes a viscosity increase that seems to be due to hydrogen bonding with the metal oxide fine particles at a low temperature. It is a polysaccharide that causes an increase in viscosity at 15 ° C. of 1.0 mPa ⁇ s or more by addition, preferably 5.0 mPa ⁇ s or more, more preferably 10.0 mPa ⁇ s or more. Polysaccharides.
  • Examples of the thickening polysaccharide applicable to the present invention include galactan (eg, agarose, agaropectin, etc.), galactomannoglycan (eg, locust bean gum, guaran, etc.), xyloglucan (eg, tamarind gum, etc.), Glucomannoglycan (eg, salmon mannan, wood-derived glucomannan, xanthan gum, etc.), galactoglucomannoglycan (eg, softwood-derived glycan), arabinogalactoglycan (eg, soybean-derived glycan, microorganism-derived glycan, etc.), Red algae such as glucuronoglycan (eg gellan gum), glycosaminoglycan (eg hyaluronic acid, keratan sulfate etc.), alginic acid and alginates, agar, ⁇ -carrageenan, ⁇ -carrageenan,
  • Such polysaccharides include, for example, pentoses such as L-arabitose, D-ribose, 2-deoxyribose, and D-xylose, and hexoses such as D-glucose, D-fructose, D-mannose, and D-galactose only. It is preferable that it is a polysaccharide.
  • tamarind seed gum known as xyloglucan whose main chain is glucose and side chain is glucose
  • guar gum known as galactomannan whose main chain is mannose and side chain is glucose
  • cationized guar gum Hydroxypropyl guar gum
  • locust bean gum locust bean gum
  • tara gum arabinogalactan whose main chain is galactose and whose side chain is arabinose
  • tamarind, guar gum, cationized guar gum, and hydroxypropyl guar gum are particularly preferable.
  • aqueous binder resins include polymers having reactive functional groups, such as polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer.
  • Acrylic resins such as polymers, vinyl acetate-acrylic acid ester copolymers, or acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic Styrene acrylic resin such as acid ester copolymer, styrene- ⁇ -methylstyrene-acrylic acid copolymer, or styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-sodium styrenesulfonate copolymer Polymer, styrene-2-hydroxy Ethyl acrylate copolymer, styrene-2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer
  • the hydrophobic binder resin in the present invention refers to a resin having a dissolution amount of less than 1.0 g at a liquid temperature of 25 ° C. with respect to 100 g of water, more preferably a resin having a dissolution amount of less than 0.5 g. More preferably, it is a resin having a dissolution amount of less than 0.25 g.
  • the hydrophobic binder resin is preferably a resin obtained by polymerizing in the curing process using a hydrophobic polymer or a monomer of the hydrophobic binder resin.
  • hydrophobic polymer examples include polyethylene, polypropylene, ethylene-propylene copolymer, olefin-based polymer such as poly (4-methyl-1-pentene), acrylate-based copolymer; Halogen-containing polymers such as vinyl and chlorinated vinyl resins; Styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer; polyethylene terephthalate, poly Polyesters such as butylene terephthalate and polyethylene naphthalate; polyamides such as nylon 6, nylon 66 and nylon 610; polyacetal; polycarbonate; polyphenylene oxide; polyphenylene sulfide; Polysulfone; Polysulfone; Polyethersulfone; Polyoxybenzylene; Polyamideimide; ABS resin (acrylonitrile), acrylate
  • hydrophobic binder resin a resin that uses a monomer of a hydrophobic binder resin and is polymerized in a curing treatment step can be exemplified, and its representative hydrophobic binder resin material Is a compound that is cured by irradiation with active energy rays, and specifically includes a radical polymerizable compound that is cured by a polymerization reaction with radical active species and a cationic polymerizable compound that is cured by a cationic polymerization reaction with cationic active species. be able to.
  • radical polymerizable compound examples include a compound having an ethylenically unsaturated bond capable of radical polymerization.
  • examples of the compound having an ethylenically unsaturated bond capable of radical polymerization include acrylic acid, methacrylic acid, itaconic acid, and crotonic acid.
  • Unsaturated carboxylic acids such as isocrotonic acid and maleic acid and their salts, esters, urethanes, amides and anhydrides, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated urethanes, etc. These radically polymerizable compounds are mentioned.
  • cationic polymerizable compound various known cationic polymerizable monomers can be used.
  • epoxies exemplified in JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, JP-A-2001-220526
  • Compounds vinyl ether compounds, oxetane compounds and the like.
  • photopolymerization initiator it is preferable to contain a photopolymerization initiator together with the above compound.
  • a photopolymerization initiator any known photopolymerization initiators published in “Application and Market of UV / EB Curing Technology” (CMC Publishing Co., Ltd., edited by Yoneho Tabata / edited by Radtech Research Association) may be used. it can.
  • an optical functional layer forming coating solution containing each constituent material and a solvent dispersion containing vanadium dioxide fine particles is applied on, for example, a transparent substrate, and thereafter, an activity such as ultraviolet rays or electron beams is applied. Irradiate energy rays.
  • ultraviolet LED ultraviolet laser
  • mercury arc lamp xenon arc lamp
  • low-pressure mercury lamp fluorescent lamp
  • carbon arc lamp tungsten-halogen copying lamp
  • sunlight can be used.
  • an electron beam it is usually cured with an electron beam having an energy of 300 eV or less, but it can also be cured instantaneously with an irradiation dose of 1 to 5 Mrad.
  • the transparent base material has a hybrid structure that also serves as an optical functional layer
  • a solvent dispersion containing vanadium dioxide fine particles in a hydrophobic resin that is a constituent material of the transparent base material And a solvent is added and dissolved to prepare a dope for film formation, and then the optical film can be suitably formed by the solution casting method used in the conventional film formation using the dope. it can.
  • hydrophobic binder resin examples include resin materials that are conventionally used in the formation of optical films, such as polyethylene, polypropylene, cellulose diacetate, cellulose triacetate (abbreviation: TAC), Cellulose acetate butyrate, cellulose acetate propionate (abbreviation: CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate and their derivatives, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate (Abbreviation: PC), norbornene resin, polymethylpentene, polyether ketone, polyimide, polyethersulfone (abbreviation: PES), polyphenylenes Fido, Polysulfones, Polyetherimide, Polyetherketoneimide, Polyamide, Fluororesin, Nylon, Polymethylmethacrylate, Acrylic and polyarylates, Arton (trade name
  • the solvent is not particularly limited, and examples thereof include methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2- Trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2- Examples include propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, and the like.
  • a hybrid optical functional layer that also serves as a transparent substrate is formed by a solution casting method.
  • additives for optical functional layers Various additives that can be applied to the optical functional layer according to the present invention as long as the effects of the present invention are not impaired are listed below.
  • nonionic surfactants JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-219266.
  • Optical brighteners sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, etc.
  • Lubricants such as tylene glycol, antiseptics, antifungal agents, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, thickeners, lubricants, infrared absorption Examples include various known additives such as agents, dyes, and pigments.
  • an aqueous binder resin After preparing vanadium dioxide fine particles by an aqueous synthesis method, without passing through a drying step, in a state of dispersion in which vanadium dioxide fine particles are present without being associated, A water-based binder resin solution prepared by dissolving a water-based binder resin in a water-based solvent is mixed to prepare a water-based optical functional layer-forming coating solution, and this optical functional layer-forming coating solution is transparent by a wet coating method. A method of forming an optical functional layer by applying and drying on a substrate is preferred.
  • vanadium dioxide fine particles are prepared in the same manner as when an aqueous binder resin is used. After that, without passing through the drying step, a solvent dispersion containing vanadium dioxide fine particles is prepared by a solvent substitution step, and then mixed and dissolved with a hydrophobic binder resin or the like to form a non-aqueous optical functional layer forming coating A method is preferred in which a liquid is prepared, and this non-aqueous coating solution for forming an optical functional layer is applied on a transparent substrate by a wet coating method and dried to form an optical functional layer.
  • the wet coating method used for forming the optical functional layer 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 curtain coating method, or US Pat. No. 2,761,419. Examples thereof include a slide hopper coating method and an extrusion coating method described in the specification, US Pat. No. 2,761791.
  • a solution casting method can be applied as a method of forming a hybrid optical functional layer that also serves as a transparent substrate.
  • a solution casting method for example, Japanese Patent Application Laid-Open No. 2013-067074, Solution casting film forming methods described in JP 2013-123868 A, JP 2013-202979 A, JP 2014-0669958 A, JP 2014-095729 A, JP 2014-159082 A, etc. Can be formed according to
  • the transparent substrate applicable to the present invention 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 impart flexibility and suitability for production (manufacturing process suitability). From the viewpoint, a transparent resin film is preferable.
  • “Transparent” 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% or more.
  • the thickness of the transparent substrate according to the present invention 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 followability to the curved glass surface when bonded to the glass substrate is improved. .
  • the transparent substrate according to the present invention is preferably a biaxially oriented polyester film, but an unstretched or at least one stretched polyester film 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.
  • the transparent substrate according to the present invention 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 optical functional 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 of the present invention is not particularly limited as long as it is transparent, but various resin films are preferably used.
  • polyolefin films for example, cycloolefin, polyethylene, polypropylene) Etc.
  • polyester films for example, polyethylene terephthalate, polyethylene naphthalate, etc.
  • polyvinyl chloride, triacetyl cellulose films and the like can be used, and cycloolefin films, polyester films, and triacetyl cellulose films are preferable.
  • undercoat layer coating solution inline on one side or both sides in the film forming process.
  • undercoating during the film forming process is referred to as in-line undercoating.
  • the dye or pigment according to the present invention contains vanadium dioxide.
  • the colorant layer may be contained as an adjacent layer in direct contact with the optical functional layer.
  • the binder of the colorant layer for example, the aforementioned hydrophobic binder resin can be used.
  • the above-described dye or pigment according to the present invention is applied to the hard coat layer as in the layer configuration of (1) or (6) (see FIG. 1A or 1F). You may make it contain.
  • an inorganic material typified by polysiloxane, an active energy ray curable resin, or the like can be used.
  • the inorganic material needs to be moisture-cured (from room temperature to warming), and it is preferable to use an active energy ray-curable resin in the present invention from the viewpoint of curing temperature, curing time, and cost.
  • the active energy ray resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams.
  • the active energy ray curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin layer is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. It is formed.
  • an active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.
  • an ultraviolet curable urethane acrylate resin for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used. Of these, ultraviolet curable acrylate resins are preferred.
  • UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in products obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It is easily obtained by reacting an acrylate monomer having a hydroxy group such as 2-hydroxypropyl acrylate.
  • An ultraviolet curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid with a hydroxyl group or carboxy group at the end of the polyester (see, for example, JP Sho 59-151112).
  • the ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.
  • ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipenta.
  • examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.
  • An adhesion layer is a layer for making it adhere to the optical film of this invention, another base material, etc.
  • the optical film of this invention When using the optical film of this invention as a window film, it is a layer for making it adhere to a window glass.
  • the above-described dye or pigment according to the present invention is directly applied to the optical functional layer containing vanadium dioxide. You may make it contain in an adhesion layer as an adjacent layer which contacts.
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer is selected from rubber-based, acrylic-based, silicon-based and urethane-based pressure-sensitive adhesives. Acrylic and silicon-based materials are preferred because yellowing does not occur over time, and acrylic-based materials are most preferable in that a general-purpose release sheet can be used.
  • the thickness of the adhesive layer is preferably in the range of 5 ⁇ m to 30 ⁇ m. If it is 5 ⁇ m or more, the adhesiveness is stable, and if it is 30 ⁇ m or less, the adhesive does not protrude from the side of the film and is easy to handle.
  • the type of separator (release sheet) to be attached to the adhesive layer it is possible to use a substrate such as polyester, polyethylene, polypropylene, paper, etc., which is coated with silicon, polyalkylene, or fluororesin.
  • a polyester film coated with silicon is particularly preferred.
  • the thickness of the separator is preferably in the range of 10 to 100 ⁇ m, more preferably 20 to 60 ⁇ m. If it is 10 ⁇ m or more, the film is not wrinkled by heat during coating and drying, and it is preferably 100 ⁇ m or less from the viewpoint of economy.
  • optical film of the present invention can be configured to be pasted on glass, and the glass on which this film is bonded can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like.
  • the glass bonded together can be used for other purposes.
  • the glass bonded with the film is preferably used for construction or for vehicles.
  • the glass bonded with the film can be used for a windshield, side glass, rear glass or roof glass of an automobile.
  • the glass member examples include inorganic glass and organic glass (resin glazing).
  • the inorganic glass examples include float plate glass, heat ray absorbing plate glass, polished plate glass, mold plate glass, netted plate glass, lined plate glass, and colored glass such as green glass.
  • the organic glass is a synthetic resin glass substituted for inorganic glass.
  • the organic glass (resin glazing) examples include a polycarbonate plate and a poly (meth) acrylic resin plate.
  • the poly (meth) acrylic resin plate examples include a polymethyl (meth) acrylate plate.
  • a 5% by mass aqueous solution of hydrazine hydrate (N 2 H 4 ⁇ H 2 O, manufactured by Wako Pure Chemical Industries, Ltd., special grade) was slowly added dropwise to the resulting solution to prepare a solution having a pH value of 9.2.
  • the prepared solution was put in a commercially available autoclave for hydrothermal reaction treatment (HU-25 type manufactured by Sanai Kagaku Co., Ltd.) (with a SUS body equipped with a 25 ml Teflon (registered trademark) inner cylinder) Hydrothermal reaction treatment was carried out for 24 hours at 270 ° C. for a time, and VO 2 fine particles 1 were obtained.
  • the VO 2 fine particles 1 had chromic properties, the number average primary particle size was 40 nm, and the ratio of tungsten (W) atoms to vanadium (V) atoms was 1.0%. The concentration of the finished VO 2 fine particles 1 was 3.0% by mass, and this was used as dispersion 1 of VO 2 fine particles 1.
  • the prepared solution 1 is placed in a commercially available autoclave for hydrothermal reaction treatment (HU-25 type, manufactured by Sanai Kagaku Co., which is provided with a 25 ml Teflon (registered trademark) inner cylinder in a SUS body) at 100 ° C.
  • a hydrothermal reaction treatment at 270 ° C. for 24 hours to obtain VO 2 fine particles 2.
  • the VO 2 fine particles 2 had chromic properties, the number average primary particle size was 40 nm, and 99.5 atomic% or more of the metal component was vanadium.
  • the concentration of the finished VO 2 fine particles 2 was 3.0% by mass, and this was used as the dispersion 2 of VO 2 fine particles 2.
  • Optical functional layer forming coating solution 1 Dispersion 1 of 3% by weight of VO 2 fine particles 1 10 parts by weight Aqueous solution of 4% by weight of hydroxypropylmethylcellulose (Metroose 60SH-50, manufactured by Shin-Etsu Chemical Co., Ltd.) 75 parts by weight 5% by weight of a surfactant aqueous solution (Triton X- 100, manufactured by Sigma-Aldrich) 2 parts by mass Pure water 13 parts by mass
  • optical film 102 was produced in the same manner as in the production of the optical film 101 except that the optical functional layer forming coating solution 1 was changed to the following optical functional layer forming coating solution 2.
  • Optical functional layer forming coating solution 2 Dispersion 2 of 3% by mass of VO 2 fine particles 2 10 parts by mass Aqueous solution of 4% by mass of hydroxypropylmethylcellulose (Metroose 60SH-50, manufactured by Shin-Etsu Chemical Co., Ltd.) 75 parts by mass 5% by mass of a surfactant aqueous solution (Triton X- 100, manufactured by Sigma-Aldrich) 2 parts by mass Pure water 13 parts by mass
  • (Colorant dispersion 1) 1 part by mass of copper phthalocyanine fine particles (manufactured by Dainichi Seika Kogyo Co., Ltd., Blue No. 84, PB-15: 3, maximum absorption wavelength 630 nm, 720 nm), methyl ethyl ketone 10 of polymethyl methacrylate (VB-7103, manufactured by Mitsubishi Rayon Co., Ltd.) 36 parts by mass of a mass% solution was dispersed with a super apex mill manufactured by Kotobukisha using zirconia beads until the average particle size was 30 nm, whereby Colorant Dispersion Liquid 1 was obtained.
  • (Colorant layer forming coating solution 1) 45 parts by weight of the colorant dispersion 1 and 30 parts by weight of methyl isobutyl ketone were mixed to obtain a coating liquid 1 for forming a colorant layer.
  • Optical Films 104 to 110 Invention
  • Optical Film 111 Comparative Example
  • an average light absorption rate at a film temperature of 23 ° C. within a light wavelength range of 650 to 700 nm is 30.
  • Optical films 104 to 111 were produced in the same manner except that the coating amount was adjusted to be 40%, 40%, 50%, 60%, 70%, 80%, 85%, and 90%.
  • the following coating solution 2 for forming a colorant layer is applied to the opposite surface of the optical functional layer formed from the coating solution 2 for forming an optical functional layer with a polyethylene terephthalate film interposed therebetween using an extrusion coater.
  • the wet coating was carried out by adjusting the coating amount so that the average light absorptance within the light wavelength range of 650 to 700 nm at a film temperature of 23 ° C. was 50%, followed by drying at 90 ° C. for 1 minute.
  • the coating film is cured by irradiating ultraviolet rays under the conditions of an illuminance of 100 mW / cm 2 , an irradiation amount of 0.2 J / cm 2 , and an oxygen concentration of 200 ppm, and coloring that also serves as a hard coat layer
  • the agent layer was formed, and the optical film 112 was produced.
  • Colorant layer forming coating solution 2 Colorant dispersion 1 315 parts by weight Aronix (registered trademark) M-305 (3, 4 functional acrylate, 3 functional component 60% by mass, manufactured by Toagosei Co., Ltd.) 196 parts by mass EBECRYL (registered trademark) 350 (bifunctional silicon acrylate, manufactured by Daicel Ornex Co., Ltd.) MIBK (methyl isobutyl ketone) diluent (1% by mass) 18 parts by weight hexoate cobalt 8% (metal soap, manufactured by Toei Chemical Co., Ltd.) 3 parts by weight Irgacure (registered trademark) 184 (photopolymerization initiator, manufactured by BASF Corporation) 13 parts by mass MegaFac (registered trademark) F-552 (surfactant, manufactured by DIC Corporation) MIBK (methyl isobutyl ketone) diluent (1% by mass) 9 parts by mass MIBK (methyl isobutyl
  • methylene chloride was added as a solvent. 100% by volume was subjected to solvent replacement treatment three times to prepare a dispersion 3 of solvent-based VO 2 fine particles 2 having a particle concentration of 3% by mass, and filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. .
  • the following methylene chloride was added to the pressure dissolution tank.
  • this dispersion was concentrated again to 20% by volume, and then methyl ethyl ketone was added as a solvent to make 100% by volume, and the solvent substitution treatment was performed twice, so that the solvent concentration of VO 2 fine particles 2 having a particle concentration of 3% by mass was obtained.
  • a dispersion 4 was prepared. (Coating liquid 1 for forming colorant layer and optical functional layer) Colorant dispersion liquid 1 37 parts by mass Dispersion liquid 4 of VO 2 fine particles 2 33 parts by mass was mixed to prepare a coating liquid 1 for forming a colorant layer / optical function layer.
  • An optical film 115 was prepared in the same manner as in the production of the optical film 106 except that the dispersion time of the colorant dispersion 1 was changed so that the average particle diameter of the particles was 60 nm.
  • the colorant dispersion 1 was changed to YMF-02A (18% by mass Cs 0.33 WO 3 dispersion, 10% by mass dispersant, average particle size 50 nm, methyl isobutyl ketone solvent, Sumitomo Metal Mining Co., Ltd.
  • the optical film 117 was produced in the same manner except that the absorption wavelength peak was changed over a wide range from 880 to 2200 nm.
  • the colorant layer / adhesive layer forming coating solution 1 described below is directly adjacent to the optical functional layer formed from the optical functional layer forming coating solution 2, using an extrusion coater.
  • Wet coating was performed by adjusting the coating amount so that the average light absorption rate within the light wavelength range of 650 to 700 nm at 23 ° C. was 40%, 50%, 70%, and 80%, respectively, Air was blown for 2 minutes to dry to form a colorant layer also serving as an adhesive layer, and optical films 119 to 122 were produced.
  • Colorant dispersion 2 1 part by mass of copper phthalocyanine fine particles (manufactured by Dainichi Seika Kogyo Co., Ltd., cyanine blue 4933GN-EP, PB-15: 4, maximum absorption wavelength 640 nm, 740 nm), methyl ethyl ketone of polymethyl methacrylate (VB-7103, manufactured by Mitsubishi Rayon Co., Ltd.) 36 parts by mass of a 10% by mass dissolving solution was dispersed with a super apex mill manufactured by Kotobukisha using zirconia beads until the number average primary particle size became 30 nm to obtain a colorant dispersion 2.
  • Colorant layer / adhesive layer forming coating solution 1 78 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of butyl acrylate, 7 parts by mass of 2-hydroxyethyl acrylate and 3 parts by mass of acrylic acid were dissolved in toluene (solid content concentration: 33% by mass), and polymerization initiator Using benzoyl peroxide (5% by mass with respect to the monomer) as a radical polymerization at 83 ° C. for 240 minutes, a polymer solution having a solid content concentration of 33% by mass (weight average molecular weight 550,000) was obtained.
  • the following colorant layer forming coating solution 2 was directly adjacent to the optical function layer formed from the optical function layer forming coating solution 2 using an extrusion coater at a film temperature of 23 ° C.
  • the colorant layer is prepared by adjusting the coating amount so that the average light absorptance in the light wavelength range of 650 to 700 nm is 50%, performing wet coating, and then blowing hot air of 90 ° C. for 2 minutes for drying.
  • To form an optical film 124. (Colorant layer forming coating solution 2) 1 part by mass of copper phthalocyanine fine particles (Daiichi Seika Kogyo Co., Ltd., Blue No.
  • the spectral transmittance of the produced optical film 116 at an optical wavelength of 1300 nm was less than 50% at a film temperature of 23 ° C., and the other optical films were 50% or more.
  • the produced optical film 123 is used in combination with a pigment that absorbs green, the spectral transmittance at a light wavelength of 550 nm is in the range of 30 to 60% at a film temperature of 23 ° C. there were.
  • the other optical films were out of the range of 30 to 60%.
  • the optical film 119 to 122 has a size of 15 mm ⁇ 20 cm of a glass plate having a thickness of 1.3 mm (manufactured by Matsunami Glass Industry Co., Ltd., “slide glass white edge polishing”), and a colorant layer that also serves as an adhesive layer.
  • the optical film was bonded using a transparent adhesive sheet (manufactured by Nitto Denko Corporation, LUCIACS CS9621T).
  • Copper Pc-A Copper phthalocyanine fine particles (Daiichi Seika Kogyo Co., Ltd., Blue No. 84, PB-15: 3, maximum absorption wavelength 630 nm, 720 nm)
  • Copper Pc-B Copper phthalocyanine fine particles (manufactured by Dainichi Seika Kogyo Co., Ltd., cyanine blue 4933GN-EP, PB-15: 4, maximum absorption wavelengths 640 nm, 740 nm)
  • CI solvent C.I. I.
  • Solvent Blue 63 (1-methylamino-4-[(3-methylphenyl) amino] -9,10-anthraquinone, maximum absorption wavelength 645 nm)
  • Green pigment Cromophtal Pink PT (CI Pigment Red 122, manufactured by BASF)
  • CWO Cs 0.33 WO 3
  • the optical film of the present invention is better than the optical film of the comparative example in terms of heat insulation for summer, heat for spring, and heat for winter. It is recognized that
  • the present invention controls the transition and fully exhibits the effect of thermodynamics without losing the large change width of the near-infrared light shielding rate and transmittance before and after the transition of vanadium dioxide.
  • it is suitable for providing an optical film that can exhibit heat-shielding properties when the feeling of galling is strong even at low temperatures.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)

Abstract

La présente invention aborde le problème consistant à obtenir un film optique contenant du dioxyde de vanadium et permettant de commander le degré de protection contre la lumière du proche infrarouge en fonction de l'environnement de température. Dans le film optique, la transition du dioxyde de vanadium peut être commandée sans sacrifier les changements importants du degré de protection et du degré de transmission de la lumière du proche infrarouge à travers la transition. Ainsi, l'effet de propriétés thermochromiques peut être suffisamment démontré, et le film optique peut être amené à présenter des propriétés de protection contre la chaleur lorsque la température est basse mais il grésille. Le film optique contient de fines particules de dioxyde de vanadium ayant des propriétés thermochromiques, et est caractérisé en ce qu'il contient un colorant ou un pigment qui absorbe la lumière ayant des longueurs d'ondes dans la gamme de 650 à 700 nm et en ce qu'il a une absorption de lumière moyenne à 23 °C de 30 à 85 % dans la gamme de longueurs d'ondes de lumière.
PCT/JP2016/059238 2015-03-31 2016-03-23 Film optique WO2016158620A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017509849A JPWO2016158620A1 (ja) 2015-03-31 2016-03-23 光学フィルム

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-070606 2015-03-31
JP2015070606 2015-03-31

Publications (1)

Publication Number Publication Date
WO2016158620A1 true WO2016158620A1 (fr) 2016-10-06

Family

ID=57005828

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/059238 WO2016158620A1 (fr) 2015-03-31 2016-03-23 Film optique

Country Status (2)

Country Link
JP (1) JPWO2016158620A1 (fr)
WO (1) WO2016158620A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019167876A1 (fr) * 2018-02-27 2019-09-06 Jsr株式会社 Filtre optique et dispositif utilisant le filtre optique
KR20210040075A (ko) 2018-08-07 2021-04-12 미쯔비시 케미컬 주식회사 광학 필름, 필름 적층체, 디스플레이 유닛

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008020525A (ja) * 2006-07-11 2008-01-31 Japan Carlit Co Ltd:The 熱線遮蔽フィルム
US20110075243A1 (en) * 2009-09-25 2011-03-31 Dong-Gun Moon Infrared ray transmittance controlling panel including color modifying layer
WO2015030206A1 (fr) * 2013-08-30 2015-03-05 積水化学工業株式会社 Film intermédiaire pour verre feuilleté et verre feuilleté
JP2015063453A (ja) * 2013-08-30 2015-04-09 積水化学工業株式会社 合わせガラス用中間膜及び合わせガラス

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008020525A (ja) * 2006-07-11 2008-01-31 Japan Carlit Co Ltd:The 熱線遮蔽フィルム
US20110075243A1 (en) * 2009-09-25 2011-03-31 Dong-Gun Moon Infrared ray transmittance controlling panel including color modifying layer
WO2015030206A1 (fr) * 2013-08-30 2015-03-05 積水化学工業株式会社 Film intermédiaire pour verre feuilleté et verre feuilleté
JP2015063453A (ja) * 2013-08-30 2015-04-09 積水化学工業株式会社 合わせガラス用中間膜及び合わせガラス

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019167876A1 (fr) * 2018-02-27 2019-09-06 Jsr株式会社 Filtre optique et dispositif utilisant le filtre optique
JPWO2019167876A1 (ja) * 2018-02-27 2021-02-25 Jsr株式会社 光学フィルターおよび光学フィルターを用いた装置
JP7207395B2 (ja) 2018-02-27 2023-01-18 Jsr株式会社 光学フィルターおよび光学フィルターを用いた装置
KR20210040075A (ko) 2018-08-07 2021-04-12 미쯔비시 케미컬 주식회사 광학 필름, 필름 적층체, 디스플레이 유닛

Also Published As

Publication number Publication date
JPWO2016158620A1 (ja) 2018-01-25

Similar Documents

Publication Publication Date Title
US10816829B2 (en) Optical film and method for producing optical film
WO2016017604A1 (fr) Film optique et procédé de fabrication d'un film optique
WO2014156822A1 (fr) Verre feuilleté
JP5994849B2 (ja) 合わせガラス
WO2014162864A1 (fr) Verre feuilleté de protection contre les rayons thermiques et son procédé de production
WO2016017611A1 (fr) Procédé pour produire des particules contenant du dioxyde de vanadium, particules contenant du dioxyde de vanadium, dispersion et film optique
JPWO2013111735A1 (ja) 光学フィルム
JP6384247B2 (ja) 光学フィルム及び光学フィルムの製造方法
WO2016006388A1 (fr) Film optique
WO2017104313A1 (fr) Film optique
WO2015146674A1 (fr) Film optique et film de fenêtre l'employant
JPWO2014199872A1 (ja) 赤外遮蔽フィルムおよびこれを用いた赤外遮蔽体および熱線反射合わせガラス
WO2015115329A1 (fr) Film optique
JP6428608B2 (ja) 赤外線遮蔽フィルム、赤外線遮蔽フィルムの設置方法及び赤外線遮蔽フィルムの虹彩防止方法
JP6465117B2 (ja) 光学フィルムの製造方法
WO2016158620A1 (fr) Film optique
JP5853431B2 (ja) 赤外遮蔽フィルムの製造方法
WO2018092502A1 (fr) Composition thermochromique et film thermochromique
WO2017077797A1 (fr) Film thermochromique et corps composite thermochromique
WO2015040896A1 (fr) Film réfléchissant stratifié et son procédé de production, et corps de blocage infrarouge comprenant ledit film
WO2017006767A1 (fr) Dispersion aqueuse de particules de dioxyde de vanadium, procédé de production de dispersion aqueuse de particules de dioxyde de vanadium, film thermochrome et complexe thermochrome
WO2017073183A1 (fr) Film thermochrome et procédé de production d'un film thermochrome
JP2017203965A (ja) ロール状の光学反射フィルム
WO2016158603A1 (fr) Procédé de production d'une particule contenant du dioxyde de vanadium rutile et procédé de production d'un film optique
WO2015060305A1 (fr) Corps de protection contre le proche infrarouge et film de protection contre le proche infrarouge

Legal Events

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

Ref document number: 16772501

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017509849

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16772501

Country of ref document: EP

Kind code of ref document: A1