WO2017104313A1 - Film optique - Google Patents

Film optique Download PDF

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Publication number
WO2017104313A1
WO2017104313A1 PCT/JP2016/083342 JP2016083342W WO2017104313A1 WO 2017104313 A1 WO2017104313 A1 WO 2017104313A1 JP 2016083342 W JP2016083342 W JP 2016083342W WO 2017104313 A1 WO2017104313 A1 WO 2017104313A1
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WIPO (PCT)
Prior art keywords
layer
optical film
vanadium dioxide
pigment red
containing particles
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PCT/JP2016/083342
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English (en)
Japanese (ja)
Inventor
博和 小山
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コニカミノルタ株式会社
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Priority to JP2017556417A priority Critical patent/JPWO2017104313A1/ja
Publication of WO2017104313A1 publication Critical patent/WO2017104313A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor

Definitions

  • the present invention relates to an optical film, and more particularly to an optical film containing vanadium dioxide-containing particles capable of adjusting the near-infrared light shielding rate in accordance with a temperature environment and hardly affected by the use environment.
  • 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.
  • the mid to high latitude winter seasons conversely, there is a problem that sunlight is shielded when it is desired to take it into the vehicle or the room as much as possible.
  • thermochromic material that controls the optical properties of near-infrared light shielding and transmission to the near-infrared light shielding film.
  • 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. That is, the optical film using the characteristics of VO 2 can exhibit characteristics such as shielding near infrared light that causes heat at high temperatures and transmitting near infrared light at low temperatures. .
  • the summertime is hot, near-infrared light is shielded to suppress the temperature rise in the room, and when the wintertime is cold, light energy can be taken in.
  • thermochromic film can be provided by forming a VO 2 dispersed resin layer in which a VO 2 particle produced by hydrothermal synthesis is dispersed in a transparent resin on a transparent substrate to form a laminate. (For example, see Patent Document 2).
  • thermochromic film When such a thermochromic film is attached to a window and used in a place where the air conditioner wind (cold air) directly hits it, the temperature rise is suppressed even when it is originally intended to block near-infrared light. In some cases, the expected performance does not function due to the influence of the usage environment, such as the fact that it is not shielded.
  • the present invention has been made in view of the above-described problems and situations, and its solution is an optical film containing vanadium dioxide-containing particles capable of adjusting the near-infrared light shielding rate according to the temperature environment, and used. It is to provide an optical film that is not easily affected by the environment.
  • the present inventor has at least one transparent heat insulating layer on the side opposite to the transparent base material of the optical functional layer in the process of examining the cause of the above-mentioned problem.
  • the present inventors have found that an optical film that is not easily affected by the above can be provided, and have reached the present invention.
  • An optical film having an optical functional layer containing vanadium dioxide-containing particles having thermochromic properties on a transparent substrate An optical film comprising at least one transparent heat insulating layer on the side of the optical functional layer opposite to the transparent substrate.
  • the transparent substrate or the transparent heat insulating layer, or the layer between the transparent substrate and the transparent heat insulating layer contains a dye or pigment that absorbs light within a light wavelength range of 400 to 700 nm.
  • Item 3. The optical film according to item 1 or 2, which is characterized.
  • the average optical absorptance of the optical film in the light wavelength range of 400 to 700 nm is in the range of 20 to 80% at 23 ° C., any one of items 1 to 3
  • the optical film of the present invention has an optical functional layer in which vanadium dioxide-containing particles having thermochromic properties are contained on a transparent substrate, and at least 1 on the opposite side of the optical functional layer from the transparent substrate. It has the transparent heat insulation layer of a layer, It is characterized by the above-mentioned. This makes it possible to provide an optical film that is not easily affected by the use environment.
  • the transparent base material, the optical functional layer, and the transparent heat insulation layer are laminated in this order so as to sandwich the optical function layer, so that the transparent base material and the transparent heat insulation layer serve as a buffer, and are used for the optical function layer.
  • the effect of the environment is suppressed, and it is thought that the chromic property can be switched according to the degree of heating of the optical functional layer by sunlight.
  • Schematic sectional view showing a basic configuration example of the optical film of the present invention Schematic sectional view showing a basic configuration example of the optical film of the present invention
  • Schematic sectional view showing a basic configuration example of the optical film of the present invention Schematic sectional view showing a basic configuration example of the optical film of the present invention
  • Schematic sectional view showing a basic configuration example of the optical film of the present invention Schematic sectional view showing a basic configuration example of the optical film of the present invention
  • Schematic sectional view showing a basic configuration example of the optical film of the present invention Schematic sectional view showing a basic configuration example of the optical film of the present invention
  • Schematic sectional view showing a basic configuration example of the optical film of the present invention Schematic process drawing showing an example of a solvent replacement processing apparatus applicable to the present invention
  • the optical film of the present invention has an optical functional layer containing vanadium dioxide-containing particles having thermochromic properties on a transparent substrate, and at least one layer on the opposite side of the optical functional layer from the transparent substrate. It has a transparent heat insulation layer. This feature is a technical feature common to the claimed invention.
  • the thermal resistance of the transparent heat insulating layer is within the range of 1.0 ⁇ 10 ⁇ 4 to 2.5 ⁇ 10 ⁇ 3 m 2 ⁇ K / W because it is not easily affected by the use environment. Preferably there is.
  • the transparent substrate or the transparent heat insulating layer, or the layer between the transparent substrate and the transparent heat insulating layer contains a dye or pigment that absorbs light in the light wavelength range of 400 to 700 nm.
  • Dye or pigment that absorbs light within the light wavelength range of 400-700 nm is heated by absorbing sunlight, and heat is transferred to the optical functional layer containing vanadium dioxide-containing particles. The chromic switching according to the heating degree of sunlight can be performed more effectively without receiving the light.
  • the average light absorption rate of the optical film within the light wavelength range of 400 to 700 nm is 23 ° C. It is preferably in the range of 20 to 85%.
  • ⁇ representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • the optical film of the present invention has an optical functional layer containing vanadium dioxide-containing particles having thermochromic properties on a transparent substrate, and at least one layer on the opposite side of the optical functional layer from the transparent substrate. It has the transparent heat insulation layer of this.
  • transparent means that the average light transmittance in the visible light region is 30% or more, preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more. is there.
  • a dye or pigment that absorbs light in the light wavelength range of 400 to 700 nm is formed in the transparent base material or the transparent heat insulating layer, or the layer between the transparent base material and the transparent heat insulating layer. It is a preferable aspect that it is contained.
  • the dye or pigment that absorbs light in the light wavelength range of 400 to 700 nm is not particularly limited as long as it is a material that absorbs light in the range of 400 to 700 nm, but it is maximum within the range of 350 to 750 nm.
  • a dye or pigment having an absorption wavelength is more preferable because it can efficiently absorb light in the range of 400 to 700 nm.
  • the “dye” 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.
  • specific examples of the dye having the maximum absorption wavelength in the light wavelength range of 350 to 750 nm include anthraquinone dyes, phthalocyanine dyes, triphenylmethane dyes, triarylmethane dyes, and indigo dyes. Etc.
  • pigments compounds classified as pigments in the color index (CI; issued by The Society of Dyersand Colorists), specifically, the following color index (CI) numbers are given. Can be mentioned.
  • Pigment red 52 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1, C.I. I.
  • Pigment red 97 C.I. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I.
  • the phthalocyanine C.I. I. Pigment blue 15: 3 (maximum absorption wavelength: 630 nm, 720 nm), C.I. I. Pigment Blue 15: 4 (maximum absorption wavelength: 640 nm, 740 nm), C.I. I. Pigment Blue 16 (maximum absorption wavelength: 620 nm, 690 nm) or the like can be preferably used.
  • the optical film of the present invention preferably has an average light absorptance within the range of 20 to 80% at 23 ° C. within the light wavelength range of 400 to 700 nm.
  • the average light absorptance (%) within the light wavelength range of 400 to 700 nm can be determined as follows.
  • Average light absorptance (%) within the light wavelength range of 400 to 700 nm 100- ⁇ (Average spectral transmittance in the range of light wavelength 400 to 700 nm)-(Average spectral reflectance in the range of light wavelength 400 to 700 nm) ⁇
  • the average spectral transmittance and the average spectral reflectance can be measured using a spectrophotometer.
  • the measurement is performed using an ultraviolet-visible near-infrared spectrophotometer V-670 manufactured by JASCO Corporation. Specifically, the temperature inside the temperature-controlled room is set to 23 ° C. and 55% RH so that the temperature of the optical film as the measurement object is 23 ° C., and the optical film is allowed to stand in the temperature-controlled room for 3 hours to equilibrate. After making the state, the above measurement is performed.
  • the spectral transmittance at an optical wavelength of 1300 nm is 50% or more at 23 ° C., since the shielding effect and the transmission effect before and after the phase transition of the vanadium dioxide-containing particles can be effectively used.
  • the spectral transmittance at a light wavelength of 550 nm is preferably in the range of 20 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 liquid containing the above-mentioned 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 optical film of the present invention is characterized in that an optical functional layer containing vanadium dioxide-containing particles having thermochromic properties is sandwiched between a transparent substrate and at least one transparent heat insulating layer. To do.
  • a layer containing a dye or pigment that absorbs light in the light wavelength range of 400 to 700 nm may be provided as a colorant layer between the transparent substrate and the transparent heat insulating layer.
  • the pigment may be contained in the optical functional layer together with the vanadium dioxide-containing particles.
  • dye or a pigment may be contained in the transparent base material or the transparent heat insulation layer. From the viewpoint of efficiently transferring solar heat absorbed by the dye or pigment to the vanadium dioxide-containing particles, the dye or pigment is contained in the optical functional layer containing the vanadium dioxide-containing particles or in an adjacent layer in direct contact with the optical functional layer. (See FIGS. 1D to 1H described later.)
  • Transparent heat insulating layer / optical functional layer containing vanadium dioxide-containing particles / transparent substrate / adhesive layer see FIG. 1A
  • Clear hard coat layer / transparent heat insulating layer / optical functional layer containing vanadium dioxide-containing particles / transparent substrate / adhesive layer see FIG. 1B
  • Colorant layer / clear hard coat layer containing dye or pigment / transparent heat insulating layer / optical functional layer containing vanadium dioxide-containing particles / transparent substrate / adhesive layer see FIG. 1C
  • Clear hard coat layer / colorant layer containing a dye or pigment / transparent heat insulating layer / optical functional layer containing vanadium dioxide-containing particles / transparent substrate / adhesive layer see FIG.
  • the adhesive layer can be attached to glass or the like.
  • the configuration (5) will be described as an example.
  • An optical film 1 shown in FIG. 1E absorbs light within a wavelength range of 400 to 700 nm, an optical functional layer 3 containing thermochromic vanadium dioxide-containing particles on one surface of a transparent substrate 2.
  • a colorant layer 4 containing a dye or a pigment, a transparent heat insulating layer 5 and a clear hard coat layer 6 are laminated in this order, and an adhesive layer 7 is laminated on the other surface of the transparent substrate 2.
  • the vanadium dioxide-containing particles are present in a dispersed state in the binder resin.
  • a dye or pigment is present in a dispersed state.
  • the number average particle diameter of the primary particles of the vanadium dioxide-containing particles in the optical functional layer 3 is preferably larger than the number average particle diameter of the primary particles of the pigment particles constituting the pigment.
  • the number average particle diameter of the vanadium dioxide-containing particles in the optical functional layer 3 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. 1E.
  • the ultrathin section is photographed at 10,000 to 100,000 times using a transmission electron microscope (TEM).
  • the particle size of the primary particles of vanadium dioxide-containing particles existing as single particles in a certain region of the photographed cross section is measured.
  • the number of vanadium dioxide-containing particles to be measured is preferably in the range of 50 to 100 particles. If the vanadium dioxide-containing particles are not spherical, the projected area of the particles is converted into a circle and the diameter is taken as the particle size.
  • the number average diameter is determined for each diameter of the primary particles. Since 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 referred to as the number average particle size (nm) in the present invention. To do.
  • the number average particle size of the primary particles is preferably in the range of 5 to 100 nm.
  • the number average particle diameter of the primary particles of the pigment particles constituting the pigment is preferably in the range of 1 to 100 nm.
  • the number average particle diameter of the pigment particles can be determined, for example, by transmission electron microscope observation (TEM) of an ultrathin slice similarly to the primary particle diameter of the vanadium dioxide-containing particles.
  • optical functional layer contains vanadium dioxide-containing particles and a binder resin.
  • Vanadium dioxide-containing particles Crystalline form of vanadium dioxide-containing particles according to the present invention is not particularly limited, thermochromic (automatic dimming) from the viewpoint of efficient expression, rutile dioxide vanadium-containing particles (VO 2 containing particles) It is particularly preferable to use it.
  • the rutile vanadium dioxide-containing particles have a monoclinic structure below the phase transition temperature, they are also called M-type.
  • the vanadium dioxide-containing particles according to the present invention may contain other crystal-type vanadium dioxide-containing particles such as A-type or B-type, as long as the object is not impaired.
  • the metal component of the vanadium dioxide-containing particles is vanadium, which can exhibit good thermochromic properties. That is, when a metal other than vanadium is doped, it is sufficient if it is doped with less than 5 atomic%.
  • tungsten W
  • molybdenum Mo
  • niobium Nb
  • tantalum Ta
  • tin Sn
  • rhenium Re
  • iridium Ir
  • osmium Os
  • ruthenium Ru
  • Germanium Ge
  • Cr chromium
  • Fe iron
  • Ga gallium
  • Al aluminum
  • fluorine F
  • P phosphorus
  • the aspect ratio of the vanadium dioxide-containing particles is preferably in the range of 1.0 to 3.0.
  • the vanadium dioxide-containing particles having such characteristics have a sufficiently small aspect ratio and isotropic shape, and therefore have good dispersibility when added to a solution.
  • the single crystal since the single crystal has a sufficiently small particle size, it can exhibit better thermochromic properties than conventional particles.
  • the concentration of the vanadium dioxide-containing 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 80% by mass with respect to the total mass of the optical functional layer, more preferably. Is in the range of 5 to 60% by mass, more preferably in the range of 5 to 40% by mass.
  • a pentavalent vanadium compound such as hydrazine or oxalic acid as a raw material together with a pentavalent vanadium compound such as ammonium vanadate (NH 4 VO 3 ), or a tetravalent vanadium compound such as vanadyl sulfate as a raw material in the liquid phase
  • a aqueous synthesis method in which particles are grown while synthesizing vanadium dioxide can be mentioned.
  • the method for producing vanadium dioxide-containing particles according to the present invention is an aqueous system in which particles are grown while synthesizing vanadium dioxide-containing particles in a liquid phase in that the average primary particle size is small and variation in particle size can be suppressed.
  • a synthetic method is preferred.
  • examples of the aqueous synthesis method include a hydrothermal synthesis method and an aqueous synthesis method using a supercritical state (also referred to as a supercritical hydrothermal synthesis method). Details of the hydrothermal synthesis method will be described later. For the details of the aqueous synthesis method using the supercritical state, for example, the production methods described in paragraphs 0011 and 0015 to 0018 of JP-A-2010-58984 can be referred to. Among the aqueous synthesis methods, it is preferable to apply the hydrothermal synthesis method.
  • vanadium dioxide-containing particles if necessary, particles such as fine TiO 2 serving as the core of particle growth are added as core particles, and vanadium dioxide-containing 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 the element to be added in order to add the 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-containing particles may be subjected to a coating treatment or a surface modification treatment with a resin. Thereby, the surface of the vanadium dioxide-containing particles can be protected, and surface-modified single crystal fine particles can be obtained.
  • the surface of the vanadium dioxide-containing particles is coated with the same or the same kind of resin as the aqueous binder resin described later.
  • 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-containing 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-containing particles prepared by the aqueous synthesis method described above contains impurities such as residues generated during the synthesis process, and has an optical function. It is preferable to remove impurities at the stage of the dispersion liquid in advance because it may cause secondary agglomerated particles when the layer is formed and may cause deterioration in long-term storage of the optical functional layer.
  • the vanadium dioxide-containing particle dispersion As a method for removing impurities in the vanadium dioxide-containing particle dispersion, conventionally known means for separating foreign substances and impurities can be applied.
  • the vanadium dioxide-containing particle dispersion is subjected to centrifugal separation to contain vanadium dioxide.
  • a method of precipitating particles, removing impurities in the supernatant, adding and dispersing the dispersion medium again, or removing impurities out of the system using an exchange membrane such as an ultrafiltration membrane may be used. From the viewpoint of preventing aggregation of vanadium-containing particles, a method using an ultrafiltration membrane is most preferable.
  • Examples of the material for the ultrafiltration membrane include cellulose, polyethersulfone, and polytetrafluoroethylene (PTFE). Among these, polyethersulfone and PTFE are preferably used.
  • the solvent replacement step is composed of a concentration step of concentrating the dispersion liquid containing vanadium dioxide-containing particles, and a solvent dilution step of adding a solvent to the concentrate for dilution, and is composed of 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-containing particles.
  • concentration means used in the concentration step of the dispersion containing specific vanadium dioxide-containing 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-containing particles by replacing water, which is a medium constituting the aqueous dispersion containing vanadium dioxide-containing 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 includes a preparation tank 11 for storing the dispersion liquid 12 containing the prepared vanadium dioxide-containing particles, a solvent stock tank 17 storing a solvent 18 for dilution, and a solvent 18.
  • the ultrafiltration unit 15 is used as a concentrating means in the route of the solvent supply line 19 to be added to the adjustment kettle 11, the circulation line 13 for circulating the dispersion 12 stored in the preparation kettle 11 by the circulation pump 14, and the circulation line 13.
  • the discharge port 16 is used to discharge the medium in the dispersion to the outside of the system.
  • the dispersion liquid containing the vanadium dioxide-containing particles prepared by the above method is stored as the dispersion liquid 12 and circulated by the circulation pump 14. It 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 12.
  • the solvent dispersion containing vanadium dioxide-containing 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. % Or less. 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. If it is% or more, the change width between the near-infrared light transmittance and the near-infrared light 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 vanadium dioxide-containing particles on the oxidation prevention and the film forming property of the coexisting hydrophobic binder, and maintain the haze at a lower level. can do.
  • the change width of the near-infrared-light transmittance at the time of a temperature change and a near-infrared-light shielding rate can further be expanded, and it is preferable conditions.
  • Vivaflow 50 (effective filtration area 50 cm 2 , molecular weight cut off 5000) manufactured by Sartorius steady is used as a filtration membrane, and ultrafiltration is performed at a flow rate of 300 ml / min, a hydraulic pressure of 100 kPa, and room temperature (25 ° C.).
  • examples thereof include an ultrafiltration device having a filtration membrane made of polyethersulfone and having 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 is used when preparing a solvent dispersion containing vanadium dioxide-containing particles by the above solvent replacement step. It is preferable to use an aqueous binder resin when the solvent substitution step is not performed.
  • Water-based binder resin represents a resin material that dissolves 0.5 g or more with respect to 100 g of water at 20 ° C., and 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, acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid -Acrylate ester co-polymer 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-containing particles and has a high effect of preventing particle aggregation even during drying of film formation, is preferable.
  • examples thereof include celluloses, polyvinyl alcohols, and acrylic resins having a hydroxy group.
  • polyvinyl alcohols and celluloses can be most preferably used.
  • polyvinyl alcohols As polyvinyl alcohols preferably used in the present invention, ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate can be used. In addition to ordinary polyvinyl alcohol, modified polyvinyl alcohols such as polyvinyl alcohols whose ends are cationically modified and anionic modified polyvinyl alcohols having an anionic group are 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 of 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 examples include 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 copolymers of vinyl alcohol and a vinyl compound having a water-soluble group, and 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, carboxymethyl cellulose (cellulose carboxymethyl ether), methyl cellulose, hydroxymethyl cellulose, Examples thereof include water-soluble cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose, carboxymethyl cellulose (cellulose carboxymethyl ether) and carboxyethyl cellulose, which are carboxylic acid group-containing celluloses. Other examples include cellulose derivatives such as nitrocellulose, cellulose acetate propionate, cellulose acetate, and cellulose sulfate.
  • the aqueous 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 hydroxy units. 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 conventionally used widely in the field of silver halide photographic light-sensitive materials can be applied, such as acid-processed gelatin and alkali-processed gelatin.
  • enzyme-treated gelatin and gelatin derivatives that undergo enzyme treatment in the gelatin production process that is, groups having amino groups, imino groups, hydroxy groups, carboxy groups as functional groups in the molecule, and groups obtained by reaction with them. It may be modified by treating with a reagent.
  • Well-known methods for producing gelatin are well known. H. James: The Theory of Photographic Process 4th. ed. Reference can be made to descriptions such as 1977 (Maccillan), p. 55, Science Photo Handbook (above), p. 72-75 (Maruzen), Fundamental of Photographic Engineering-Silver Salt Photo Hen, pages 119-124 (Corona). Also, Research Disclosure Magazine Vol. 176, No. And gelatin described on page IX of 17643 (December 1978).
  • 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 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 further adding metal oxide fine particles, it causes a viscosity increase caused by hydrogen bonding with the metal oxide fine particles at low temperatures, When added, it is a polysaccharide that increases its viscosity at 15 ° C. by 1.0 mPa ⁇ s or more, 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,
  • the structural unit does not have a carboxylic acid group or a sulfonic acid group.
  • polysaccharides include 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- Acrylic resins such as acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene -Methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene- ⁇ -methylstyrene-acrylic acid copolymer, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer, etc.
  • polymers having reactive functional groups such as polyvinylpyrrolidones, polyacrylic acid, acrylic acid- Acrylic resins such as acrylonitrile copolymer, potassium acrylate
  • Styrene acrylic acid resin Styrene-sodium styrene sulfonate copolymer Styrene-2-hydroxyethyl acrylate copolymer, styrene-2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid Copolymers, vinyl naphthalene-maleic acid copolymers, vinyl acetate-maleic acid ester copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-based copolymers such as vinyl acetate-acrylic acid copolymers, and the like Of the salt.
  • particularly preferred examples include polyvinylpyrrolidones and copolymers containing the same.
  • the hydrophobic binder resin 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.
  • the amount of the resin is less than 0.5 g, particularly preferably the 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 copolymers, olefin polymers such as poly (4-methyl-1-pentene), acrylate copolymers, chlorides, and the like.
  • 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, polyether ABS resin (acrylonitrile-butadiene-styrene resin), ASA resin (acrylonitrile-styrene-acrylate resin), cellulose blended with rutheketone, polysulfone, polyethersulfone, polyoxybenzylene, polyamideimide, polybutadiene rubber, acrylic rubber Resin, butyral resin, and the like.
  • hydrophobic binder resin applicable to the present invention, a resin that is polymerized in a curing process using a monomer of a hydrophobic binder resin can be exemplified, and typical hydrophobic binder resin materials include: A compound that is cured by irradiation with active energy rays, specifically 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. it can.
  • 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.
  • cationic polymerizable monomers JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like exemplified in JP-A-2001-220526.
  • photopolymerization initiators all known photopolymerization initiators listed in “Application and Market of UV / EB Curing Technology” (CMC Publishing Co., Ltd., edited by Yoneho Tabata / edited by Radtech Research Association) should be used. Can do.
  • 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.
  • optical 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-61-228771, 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, and polyethylene Lubricants such as glycol, antiseptics, antifungal agents, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, lubricants, infrared absorbers And various known additives such as dyes and pigments.
  • Lubricants such as glycol, antiseptics, antifungal agents, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, lub
  • an aqueous binder resin After preparing vanadium dioxide-containing particles by an aqueous synthesis method, a state of a dispersion in which vanadium dioxide-containing particles exist without being associated with each other without passing through a drying step. Then, by mixing an aqueous binder resin solution prepared by dissolving an aqueous binder resin in an aqueous solvent, an aqueous optical functional layer forming coating solution is prepared, and this optical functional layer forming coating solution is prepared by a wet coating method. A method of forming an optical functional layer by applying and drying on a transparent substrate is preferred.
  • vanadium dioxide-containing particles are prepared in the same manner as when an aqueous binder resin is used. After that, without passing through a drying step, a solvent dispersion containing vanadium dioxide-containing particles is prepared by a solvent substitution step, and then mixed and dissolved with a hydrophobic binder resin, etc. for forming a non-aqueous optical functional layer A method is preferred in which a coating solution is prepared, and this non-aqueous coating solution for forming an optical functional layer is applied and dried on a transparent substrate by a wet coating method 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.
  • the transparent heat-insulating layer according to the present invention is not particularly limited as long as it is transparent and has an effect of suppressing heat transfer, for example, a transparent polymer layer, a transparent porous layer, a layer containing hollow particles or porous particles, etc. Can be mentioned.
  • the thermal resistance (R) of the transparent heat insulating layer is preferably in the range of 1.0 ⁇ 10 ⁇ 4 to 2.5 ⁇ 10 ⁇ 3 m 2 ⁇ K / W. More preferably, it is in the range of 5 ⁇ 10 ⁇ 4 to 1.5 ⁇ 10 ⁇ 3 .
  • the thermal resistance of the transparent heat insulating layer (R) is 1.0 ⁇ 10 -4 m 2 ⁇ K / W or more, a large effect of preventing the influence of the external environment such as air conditioning, 2.5 ⁇ 10 - If it is 3 m ⁇ 2 > * K / W or less, when the sunlight which hits the heated optical film will become weak, it can suppress that the temperature of an optical film falls quickly and continues shielding of near-infrared light.
  • the thermal resistance (R) (m 2 ⁇ K / W) can be obtained by thickness (d) (m) ⁇ material thermal conductivity ( ⁇ ) (W / (m ⁇ K)).
  • the thickness of the transparent heat insulating layer may be appropriately set according to the constituent material (thermal conductivity ( ⁇ )) of the transparent heat insulating layer.
  • Transparent polymer layer An example of the transparent polymer layer is a transparent resin film.
  • transparent resin films include polyolefin films (eg, cycloolefin, polyethylene, polypropylene, etc.), polyester films (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, polycarbonate films, triacetylcellulose films, acrylic films. (Polymethylmethacrylate etc.) etc. can be used, Preferably it is a polyethylene terephthalate film.
  • Transparent porous layer As a method for forming the transparent porous layer, for example, a method for forming a porous layer using a sol-gel method can be used.
  • a method for forming a porous layer using a sol-gel method can be used.
  • the method for producing a porous silica material generally, alkoxysilane is hydrolyzed, and the generated silica sol is polycondensed to form a wet gel, which is dried to obtain a porous silica material.
  • the hollow particle-containing layer for example, a layer in which hollow particles described in JP-T-2000-500113, JP-A-2005-263550, JP-A-2012-144394, etc. are contained in a transparent resin is used. Can do.
  • the layer can be similarly produced by using hollow particles instead of vanadium dioxide-containing particles in the optical functional layer described above.
  • porous particle containing layer As the porous particle-containing layer, for example, it is possible to use a layer in which transparent resin contains particles obtained by atomizing methyl silicate monomer obtained by air drying by atmospheric pressure drying or critical drying.
  • JP 2013-100406 A can be referred 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.
  • the thermal resistance (R) of the transparent substrate is preferably in the range of 1.0 ⁇ 10 ⁇ 4 to 2.5 ⁇ 10 ⁇ 3 m 2 ⁇ K / W.
  • the thermal resistance (R) of the transparent substrate is 1.0 ⁇ 10 ⁇ 4 m 2 ⁇ K / W or more, the effect of preventing the influence of an external environment such as an air conditioner is great.
  • the large heat capacity of glass compared to the optical film even if the temperature of the outside air drops and there is no need to shield near-infrared light, it is possible to shield near-infrared light by the influence of the residual heat of the glass heated by the sun. The condition continued.
  • An optical film that can suppress the influence of the heat of glass because the thermal resistance (R) of the transparent substrate is 2.5 ⁇ 10 ⁇ 3 m 2 ⁇ K / W or less, and is less affected by the external environment can do.
  • 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 preferable, more preferably in the range of 1.5 to 3.0%, still 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.
  • the transparent resin film is preferably coated with an undercoat layer coating solution inline on one or both sides during the film formation process.
  • undercoating during the film forming process is referred to as in-line undercoating.
  • the dye or pigment according to the present invention is added to vanadium dioxide-containing particles. You may make it contain in a colorant layer as an adjacent layer which contacts the optical function layer in which was contained.
  • the binder of the colorant layer for example, the aforementioned hydrophobic binder resin can be used.
  • the clear hard coat layer (CHC layer) according to the present invention is a layer provided on the opposite side of the transparent heat insulating layer from the optical functional layer.
  • a dye or pigment may be included in the clear hard coat layer as in the layer configuration of (3) above (see FIG. 1C).
  • an inorganic material typified by polysiloxane, an active energy ray curable resin, or the like can be used.
  • Inorganic materials need to be moisture-cured (from room temperature to warming). From the viewpoint of curing temperature, curing time, and cost, it is preferable to use an active energy ray-curable resin in the present invention.
  • 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 and electron beams.
  • 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.
  • Typical examples of the 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.
  • UV curable acrylate resins are preferred.
  • UV curable acrylic urethane resins generally contain 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as methacrylates) in addition to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. Only acrylates are indicated as such), and can be easily obtained by reacting an acrylate monomer having a hydroxy group such as 2-hydroxypropyl acrylate.
  • a mixture of 100 parts by mass of Unidic 17-806 (manufactured by DIC Corporation) and 1 part by mass of Coronate L (manufactured by Tosoh Corporation) described in JP-A-59-151110 is preferably used.
  • 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 (See 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.
  • UV curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipenta Examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.
  • An adhesion layer is a layer for making the optical film of this invention adhere to another base material.
  • the optical film of this invention is a layer for making it adhere to a window glass.
  • a dye or pigment may be contained in the adhesive layer as in the layer configuration of (9) above (see FIG. 1I).
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer is selected from rubber-based, acrylic-based, silicone-based and urethane-based pressure-sensitive adhesives. Since there is no yellowing over time, acrylic and silicone are preferred, and acrylic is most preferred because a general-purpose release sheet can be used.
  • the thickness of the adhesive layer is preferably in the range of 5 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.
  • a substrate such as polyester, polyethylene, polypropylene, paper, etc., which is coated with silicone coat, polyalkylene coat or fluororesin can be used.
  • silicone coat polyalkylene coat or fluororesin
  • dimensional stability and smoothness can be used.
  • a polyester film coated with silicone is particularly preferred.
  • the thickness of the separator is preferably in the range of 10 to 100 ⁇ m, more preferably in the range of 20 to 60 ⁇ m. If it is 10 ⁇ m or more, the film is not wrinkled due to 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 colored glass such as float plate glass, heat ray absorbing plate glass, polished plate glass, mold plate glass, meshed plate glass, wire-containing plate glass, and green glass.
  • Organic glass is a synthetic resin glass that can be substituted for inorganic glass.
  • organic glass (resin glazing) examples include polycarbonate plates and poly (meth) acrylic resin plates.
  • the poly (meth) acrylic resin plate examples include a polymethyl (meth) acrylate plate.
  • ⁇ Preparation of dispersion of vanadium dioxide-containing particles >> ⁇ Preparation of dispersion 1 of vanadium dioxide-containing particles> 1 g of vanadate ammonium (V) (NH 4 VO 3 , Wako Pure Chemicals, special grade) is mixed with 25 g of pure water, and hydrazine monohydrate (N 2 H 4 ⁇ H 2 O, Wako Pure Chemical Industries, special grade) is mixed. ) was slowly added dropwise.
  • the prepared reaction solution is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: manufactured by Sanai Kagaku Co., Ltd.), 100 ° C.
  • the concentration of the finished vanadium dioxide-containing particles is adjusted to 3.0% by mass, and further 15 masses per 100 parts by mass of the vanadium dioxide-containing particles.
  • Polyvinylpyrrolidone (PVP, manufactured by Nippon Shokubai Co., Ltd., K-30) was added at a ratio of 1 part, and dispersed with a super apex mill manufactured by Kotobukisha using 30 ⁇ m zirconia beads to prepare a dispersion 2 of vanadium dioxide-containing particles. did.
  • V vanadate ammonium
  • NH 4 VO 3 vanadate ammonium
  • hydrazine monohydrate N 2 H 4 ⁇ H 2 O, Wako Pure Chemical Industries, special grade
  • the prepared reaction solution is placed in a high-pressure reaction decomposition vessel stationary HU 50 ml set (pressure-resistant stainless steel outer tube, PTFE sample vessel HUTc-50: manufactured by Sanai Kagaku Co., Ltd.), 100 ° C. for 2 hours, and subsequently 275 ° C.
  • the hydrothermal reaction was carried out for 24 hours.
  • an ultrafiltration apparatus having a filtration membrane made of polyethersulfone and having a molecular weight cut off of 300,000 (Pericon 2 manufactured by Nihon Millipore Corporation) with the reaction solution kept at 20 ° C. while circulating in the system.
  • Concentration operation was performed using the solvent displacement treatment apparatus shown in FIG. 2 equipped with a cassette), and when the initial volume was 100% by volume, after concentration to 20% by volume, ethyl alcohol was added and 100% by volume. It was.
  • the dispersion was concentrated again to 20% by volume, then methyl ethyl ketone was added as a solvent to make 100% by volume, and the solvent was subjected to two solvent substitution treatments.
  • the solvent-based vanadium dioxide-containing particles having a particle concentration of 3% by mass A dispersion 3 was prepared.
  • Optical functional layer forming coating solution 1 Dispersion 1 of vanadium dioxide-containing particles 1 10 parts by weight Aqueous solution of 4% by weight of hydroxypropyl methylcellulose (Metroose 60SH-50, manufactured by Shin-Etsu Chemical Co., Ltd.) 75 parts by weight 5% by weight of an aqueous surfactant solution (Triton X-100, Sigma-Aldrich) 2 parts by mass pure water 13 parts by mass
  • a clear hard coat layer forming coating solution 1 having the following composition is wet coated by adjusting the coating amount so that the dry film thickness becomes 2 ⁇ m using an extrusion coater. Dry at 1 ° C. for 1 minute.
  • the coating film was 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 to form a clear hard coat layer. .
  • An adhesive layer forming coating solution 1 having the following composition is applied on the surface opposite to the optical functional layer across the PET film so that the dry film thickness is 10 ⁇ m, and dried at 90 ° C. for 1 minute.
  • the optical film 101 was produced by forming.
  • a release film (MRF # 25, manufactured by Mitsubishi Resin Co., Ltd.) was bonded to the outermost surface on the adhesive layer side to protect the surface.
  • Coating layer forming coating solution 1 N-2147 (acrylic adhesive, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 100 parts by mass Tinuvin (registered trademark) 477 (ultraviolet absorber, manufactured by BASF Japan Ltd.) 2.1 parts by mass Coronate (registered trademark) HL (curing agent, manufactured by Tosoh Corporation) 5 parts by mass MIBK (methyl isobutyl ketone) 300 Parts by mass
  • Each surface of PET 1 for transparent heat insulation layer is subjected to a corona discharge treatment of 12 W ⁇ min / m 2 , and an easy-adhesion layer-forming coating solution 1 having the following composition is applied to a dry film thickness of 0.4 ⁇ m. 12 W ⁇ min / m 2 of corona discharge treatment, and the easy-adhesion layer-forming coating solution 2 having the following composition was applied so as to have a dry film thickness of 0.06 ⁇ m. did.
  • Copolymer latex solution (30% solid content) of 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25% by weight of 2-hydroxyethyl acrylate 50 g
  • Compound (UL-1) 0.2g Hexamethylene-1,6-bis (ethyleneurea) 0.05g 1000ml of pure water
  • the clear hard coat layer-forming coating solution 1 was applied to one surface of the transparent heat-insulating layer-coated PET 1 with the easy adhesion layer applied in the same manner as the optical film 101.
  • the adhesive layer forming coating solution 1 having the following composition is applied on the surface opposite to the surface coated with the clear hard coat layer forming coating solution 1 so that the dry film thickness is 10 ⁇ m. It dried for minutes and bonded together with the optical function layer of the PET film prepared previously.
  • Adhesive layer forming coating solution 1 N-2147 (acrylic adhesive, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 100 parts by mass Coronate (registered trademark) HL (curing agent, manufactured by Tosoh Corporation) 5 parts by mass MIBK (methyl isobutyl ketone) 300 parts by mass
  • the adhesive layer forming coating solution 1 is applied on the surface opposite to the optical functional layer across the PET film so that the dry film thickness is 10 ⁇ m, and dried at 90 ° C. for 1 minute to form the adhesive layer.
  • the optical film 102 was produced by forming.
  • a release film (MRF # 25, manufactured by Mitsubishi Resin Co., Ltd.) was bonded to the outermost surface on the adhesive layer side to protect the surface.
  • Optical films 103 to 111 were produced in the same manner as in the production of the optical film 102 except that the transparent heat insulating layer PET1 was replaced with the following transparent heat insulating layer PET.
  • the optical film 103 transparent heat insulating layer PET 2 (thickness 15 [mu] m, the thermal resistance 1.07 ⁇ 10 -4 m 2 ⁇ K / W)
  • Optical film 104 PET3 for transparent heat insulation layer (thickness 25 ⁇ m, thermal resistance 1.79 ⁇ 10 ⁇ 4 m 2 ⁇ K / W)
  • Optical film 105 PET4 for transparent heat insulation layer (thickness 50 ⁇ m, thermal resistance 3.57 ⁇ 10 ⁇ 4 m 2 ⁇ K / W)
  • Optical film 106 PET5 for transparent heat insulating layer (thickness 100 ⁇ m, thermal resistance 7.14 ⁇ 10 ⁇ 4 m 2 ⁇ K / W)
  • Optical film 107 PET6 for transparent heat insulating layer (thickness 150 ⁇ m, thermal resistance 1.07 ⁇ 10 ⁇ 3 m 2 ⁇ K / W)
  • Optical film 108 PET7 for transparent heat insulation layer (thickness 200 ⁇ m, thermal resistance 1.43
  • the addition amount of the pigment that absorbs light within the light wavelength range of 400 to 700 nm is the average light absorption rate of the optical film within the light wavelength range of 400 to 700 nm as shown in Table 1.
  • Optical films 122 to 124 were produced in the same manner except that the adjustment was performed.
  • optical film 125 was produced in the same manner as in the production of the optical film 115 except that the dispersion 2 of vanadium dioxide-containing particles was used instead of the dispersion 1 of vanadium dioxide-containing particles.
  • Optical Film 126 In the production of the optical film 115, a pigment that absorbs light within a light wavelength range of 400 to 700 nm is used as a dye. I. An optical film 126 was produced in the same manner except that the solvent was changed to Solvent Blue 63 (1-methylamino-4-[(3-methylphenyl) amino] -9,10-anthraquinone, maximum absorption wavelength 645 nm).
  • the dispersion liquid 3 of vanadium dioxide-containing particles is further added to the adhesive layer coating liquid 1 in the light wavelength range of 400 to 700 nm.
  • An optical film 127 was produced in the same manner except that the addition amount was adjusted so that the average optical absorptance of the optical film was 55%.
  • a transparent heat insulating layer containing airgel fine particles (thickness 8 ⁇ m, heat resistance 1) using a coating solution 1 for forming a transparent heat insulating layer having the following composition between the optical functional layer and the clear hard coat layer. 0.004 ⁇ 10 ⁇ 4 m 2 ⁇ K / W), an optical film 128 was produced in the same manner.
  • the thickness of the transparent heat insulating layer is 13 ⁇ m (thermal resistance 1.63 ⁇ 10 ⁇ 4 m 2 ⁇ K / W) and 20 ⁇ m (thermal resistance 2.50 ⁇ 10 ⁇ 4 m 2 ⁇ K / W), respectively.
  • Optical films 129 and 130 were produced in the same manner except that the film was changed to.
  • the optical film of the present invention is not suppressed in temperature rise even when it is used in a place where the air of the air conditioner directly hits, as compared with the optical film of the comparative example. It can be seen that near-infrared light can be effectively shielded. From the above, it has an optical functional layer containing vanadium dioxide-containing particles having thermochromic properties on a transparent substrate, and at least one transparent heat insulating layer is provided on the opposite side of the optical functional layer from the transparent substrate. It was confirmed that it was useful to provide an optical film that is hardly affected by the use environment.
  • the optical film of the present invention has a structure in which the optical functional layer containing the vanadium dioxide-containing particles is sandwiched between the transparent base material and the transparent base material, so that the glass window heated by sunlight is used. It was confirmed that the duration of the near-infrared light shielding effect can be shortened in an environment where the influence of residual heat is small and near-infrared light shielding is not required.
  • the present invention is an optical film containing vanadium dioxide-containing particles that can adjust the near-infrared light shielding rate according to the temperature environment, and is particularly preferably used for providing an optical film that is not easily affected by the use environment. can do.

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

Abstract

La présente invention vise à proposer un film optique qui contient du dioxyde de vanadium contenant des particules et n'est pas sensible à l'influence de l'environnement d'utilisation, et dans lequel le taux de protection contre la lumière infrarouge proche peut être réglé en fonction de la température ambiante. Selon la présente invention, ce film optique (1) est caractérisé : en ce qu'il comprend, sur une base transparente (2), une couche à fonction optique (3) qui contient du dioxyde de vanadium contenant des particules possédant des propriétés thermochromiques ; et en ce qu'il comprend au moins une couche d'isolation thermique transparente (5) sur une surface de la couche à fonction optique (3), cette surface se situant sur le côté opposé de la surface du côté base transparente.
PCT/JP2016/083342 2015-12-17 2016-11-10 Film optique WO2017104313A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019121650A1 (fr) 2017-12-21 2019-06-27 Lumileds Holding B.V. Dispositif d'éclairage
US11054112B2 (en) 2017-12-22 2021-07-06 Lumileds Llc Ceramic phosphor with lateral light barriers
US11489095B2 (en) 2017-12-21 2022-11-01 Lumileds Llc Method of addressing an LED array with light intensity adaptive LED sidewalls

Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH10311189A (ja) * 1997-05-09 1998-11-24 Kanegafuchi Chem Ind Co Ltd 調光ガラスおよびそれを使用してなる窓
JP2004346261A (ja) * 2003-05-26 2004-12-09 Toagosei Co Ltd サーモクロミック材料、およびそれを用いたサーモクロミックフィルムまたはサーモクロミックガラス
JP2012072039A (ja) * 2010-09-29 2012-04-12 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
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
JPH10311189A (ja) * 1997-05-09 1998-11-24 Kanegafuchi Chem Ind Co Ltd 調光ガラスおよびそれを使用してなる窓
JP2004346261A (ja) * 2003-05-26 2004-12-09 Toagosei Co Ltd サーモクロミック材料、およびそれを用いたサーモクロミックフィルムまたはサーモクロミックガラス
JP2012072039A (ja) * 2010-09-29 2012-04-12 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
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 (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019121650A1 (fr) 2017-12-21 2019-06-27 Lumileds Holding B.V. Dispositif d'éclairage
US10892387B2 (en) 2017-12-21 2021-01-12 Lumileds, LLC Lighting device with switching material
US11437553B2 (en) 2017-12-21 2022-09-06 Lumileds Llc Lighting device with switching material
US11489095B2 (en) 2017-12-21 2022-11-01 Lumileds Llc Method of addressing an LED array with light intensity adaptive LED sidewalls
US11557703B2 (en) 2017-12-21 2023-01-17 Lumileds Llc Light intensity adaptive LED sidewalls
US11791445B2 (en) 2017-12-21 2023-10-17 Lumileds Llc Lighting device with switching material
US11888100B2 (en) 2017-12-21 2024-01-30 Lumileds Llc LED array with light intensity adaptive LED sidewalls
US11054112B2 (en) 2017-12-22 2021-07-06 Lumileds Llc Ceramic phosphor with lateral light barriers
US11480315B2 (en) 2017-12-22 2022-10-25 Lumileds Llc Phosphor with light barriers

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