WO2017033533A1 - Film thermochrome et composite thermochrome - Google Patents

Film thermochrome et composite thermochrome Download PDF

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Publication number
WO2017033533A1
WO2017033533A1 PCT/JP2016/067606 JP2016067606W WO2017033533A1 WO 2017033533 A1 WO2017033533 A1 WO 2017033533A1 JP 2016067606 W JP2016067606 W JP 2016067606W WO 2017033533 A1 WO2017033533 A1 WO 2017033533A1
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thermochromic
film
particles
functional layer
optical functional
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PCT/JP2016/067606
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English (en)
Japanese (ja)
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鈴木　伸一
丈範 熊谷
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コニカミノルタ株式会社
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Priority to JP2017536644A priority Critical patent/JPWO2017033533A1/ja
Priority to CN201680048379.0A priority patent/CN107922260A/zh
Publication of WO2017033533A1 publication Critical patent/WO2017033533A1/fr

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    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy

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  • the present invention relates to a thermochromic film and a thermochromic composite. More specifically, the present invention relates to a thermochromic film containing vanadium dioxide particles having thermochromic properties.
  • the near-infrared light shielding film can be applied to a vehicle body or a window glass of a building to reduce a load on a cooling facility such as an air conditioner in the vehicle, and is an effective means for energy saving.
  • an optical film containing a conductor such as ITO (indium tin oxide) as an infrared absorbing substance is disclosed. Also, it has a near infrared light shielding film including a functional plastic film having an infrared reflection layer and an infrared absorption layer, and a reflection layer laminate in which a large number of low refractive index layers and high refractive index layers are alternately laminated.
  • a near-infrared light shielding film that selectively reflects near-infrared light by adjusting the thickness of each refractive index layer has been proposed.
  • the near-infrared light shielding film having such a configuration is preferably used due to its high near-infrared light shielding effect in a low-latitude zone near the equator where the illuminance of sunlight is high.
  • a low-latitude zone near the equator where the illuminance of sunlight is high.
  • incident light is uniformly shielded even when it is desired to capture sunlight as much as possible in the vehicle or indoors.
  • thermochromic material in which the optical properties of near-infrared light shielding and transmission are controlled by temperature has been studied.
  • a typical material is vanadium dioxide (hereinafter also referred to as “VO 2 ”).
  • VO 2 is known to undergo a phase transition in a temperature range of around 60 ° C. and exhibit thermochromic properties.
  • thermochromic film as a laminate for dispersing VO 2 particles in a transparent resin and forming a VO 2 dispersed resin layer on a resin substrate (see, for example, Patent Document 1) or doping with molybdenum or the like.
  • a method (for example, refer to Patent Document 2) of providing a thermochromic film by mixing the obtained VO 2 particles with a polyester resin by a T-die method is disclosed.
  • VO 2 particles are synthesized after the particles are filtered and dried, or using a solvent-based coating solution prepared with a binder insoluble in an aqueous solvent, an optical functional film that exhibits thermochromic properties is formed. It was found that the primary particles of the VO 2 particles tend to aggregate to form secondary particles.
  • Patent Document 3 describes that a laminated body is obtained by dispersing a thermochromic material in a water-soluble acrylic resin. However, a thermal barrier layer must be provided, and the thermochromic property is sufficient. There wasn't. Especially in winter, the heat absorbed by the variable property layer was only transferred to the room by heat transfer, which was not sufficient.
  • the present invention has been made in view of the above-described problems and circumstances, and its solution is to provide a thermochromic film and a thermochromic composite containing vanadium dioxide particles exhibiting excellent thermochromic properties and durability. It is.
  • thermochromic film of the present invention has a binder resin having a reactive functional group and water-soluble, and an optical functional layer. It was found that the film thickness and the water content of were within the predetermined ranges, and thus exhibited excellent thermochromic properties and durability, leading to the present invention. That is, the said subject of this invention is solved by the following means.
  • thermochromic film having an optical functional layer containing vanadium dioxide particles exhibiting at least thermochromic properties and a binder resin on a transparent substrate,
  • the binder resin has a reactive functional group and is water-soluble;
  • the moisture content of the optical functional layer after being left for 24 hours at 80 ° C. and 80% humidity is in the range of 0.5 to 5.0 g / m 2 , and the film thickness of the optical functional layer is 0
  • thermochromic film according to item 1 wherein the water content is in the range of 0.6 to 2.0 g / m 2 .
  • thermochromic film according to item 1 or 2 which contains a water-soluble cellulose resin as the binder resin.
  • thermo according to claim 1 wherein the optical functional layer further contains at least one of an isocyanate compound, a melamine compound, a carbodiimide compound, and an epoxy compound. Chromic film.
  • thermochromic composite comprising the thermochromic film according to any one of items 1 to 4 as a constituent element.
  • thermochromic film and a thermochromic composite containing vanadium dioxide particles exhibiting excellent thermochromic properties and durability.
  • the VO 2 particles form an optical functional film that exhibits thermochromic properties by using a solvent-based coating solution prepared by filtering and drying after synthesizing the particles or a binder insoluble in an aqueous solvent.
  • the primary particles of the VO 2 particles tend to aggregate to form secondary particles.
  • a water-soluble binder is used without adjusting the amount of water contained in the vanadium dioxide particles and stored at a high temperature and high humidity for a long time, the reduction of the vanadium dioxide particles is promoted, and the vanadium dioxide thermostat. It is considered that the chromic property is impaired or the durability of the film is lowered.
  • thermochromic film which shows the outstanding thermochromic property and durability can be provided.
  • thermochromic film of the present invention is a thermochromic film having an optical functional layer containing at least thermochromic vanadium dioxide particles and a binder resin on a transparent substrate, wherein the binder resin is a reactive functional group. And the water content of the optical functional layer after standing for 24 hours at 80 ° C. and 80% humidity is in the range of 0.5 to 5.0 g / m 2 , and The optical functional layer has a thickness in the range of 0.5 to 5.0 ⁇ m. This feature is a technical feature common to or corresponding to the claimed invention.
  • the water content is more preferably in the range of 0.6 to 2.0 g / m 2 from the viewpoint of manifestation of the effect of the present invention.
  • a water-soluble cellulose resin as the binder resin from the viewpoints of good dispersibility of vanadium dioxide particles, high thermochromic properties, low haze and flexibility.
  • the optical functional layer further contains at least one of an isocyanate compound, a melamine compound, a carbodiimide compound and an epoxy compound from the viewpoint of manifesting the effect of the present invention.
  • thermochromic complex of the present invention preferably includes the thermochromic film of the present invention as a constituent element from the viewpoint of manifesting the effects of the present invention.
  • ⁇ 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.
  • Vanadium dioxide according to the present invention is an embodiment of vanadium oxide.
  • Vanadium oxide takes various forms in nature, including V 2 O 5 , H 3 V 2 O 7 ⁇ , H 2 VO 4 ⁇ , HVO 4 2 ⁇ , VO 4 3 ⁇ , VO 2+ , VO 2 , V 3+ , V Examples of the structure include 2 O 3 , V 2+ , V 2 O 2 , and V.
  • the form changes depending on each environmental atmosphere.
  • V 2 O 5 is formed in an acidic environment
  • V 2 O 3 is formed in a reducing environment. Therefore, VO 2 is relatively easy to oxidize and reduce, and the crystal structure changes depending on the surrounding environment. Since VO 2 exhibiting thermochromic properties (automatic light control) exhibits a monoclinic structure, VO 2 used in the present invention is a monoclinic crystal.
  • the crystal form of the vanadium dioxide particles used in the present invention is preferably rutile VO 2 particles (hereinafter also simply referred to as “VO 2 particles”) from the viewpoint of efficiently expressing thermochromic properties. Since the rutile VO 2 particles have a monoclinic structure below the transition temperature, they are also called M-type.
  • the vanadium dioxide particles according to the present invention may contain VO 2 particles of other crystal types such as A-type or B-type within a range that does not impair the purpose.
  • the VO 2 particles according to the present invention are preferably present in a state where the number average particle diameter of primary particles and secondary particles is less than 500 nm in the optical functional layer.
  • Various measurement methods can be applied to the particle diameter measurement method, but it is preferable to measure according to the dynamic light scattering method.
  • the preferred number average particle diameter of the primary particles and secondary particles in the VO 2 particles according to the present invention is in the range of 1 to 200 nm, more preferably in the range of 5 to 100 nm, and most preferably in the range of 5 to 60 nm. Is within the range.
  • the aspect ratio of the VO 2 particles is preferably in the range of 1.0 to 3.0.
  • the VO 2 particles having such characteristics have a sufficiently small aspect ratio and isotropic shape, and therefore have good dispersibility when added to a solution.
  • the particle diameter of the single crystal is sufficiently small, better thermochromic properties can be exhibited compared to conventional particles.
  • a substance containing an element for adjusting the phase transition temperature of the vanadium dioxide particles may be further included.
  • the substance for adjusting the phase transition temperature is not particularly limited, but tungsten, titanium, molybdenum, niobium, tantalum, tin, rhenium, iridium, osmium, ruthenium, germanium, chromium, iron, gallium, aluminum, fluorine, phosphorus, etc. are used. it can.
  • the phase transition temperature of a vanadium dioxide particle can be lowered
  • the amount of the above substance added is not particularly limited, but is an amount that is preferably within a range of 0.03 to 1 element, more preferably 0.04 to 0.08 element with respect to 100 elements of vanadium.
  • aqueous dispersion of vanadium dioxide particles In general, synthesis of vanadium dioxide particles, a method of pulverizing the VO 2 sintered body synthesized by the solid phase method, vanadium pentoxide (V 2 O 5) as a raw material, while combining the VO 2 in the liquid phase An aqueous synthesis method in which particles are grown can be mentioned.
  • VO 2 produced by any method can be applied.
  • a dispersant is added to VO 2 produced by any method to prepare an aqueous dispersion. The amount of the dispersant added can be reduced by using water as the solvent, compared with the case of using an organic solvent, and is preferably in the range of 0.1 to 1.0% by mass.
  • dispersants include polyoxyethylene nonylphenyl ether, polyethylene ethylene laurate, hydroxy Examples thereof include ethyl cellulose, polyvinyl pyrrolidone, polyethylene glycol, and hydroxyl ethyl cellulose, and polyvinyl pyrrolidone or cellulose resin is particularly preferable. Then, without drying the VO 2 particles of the aqueous dispersion, it is possible to prepare optically functional layer forming coating solution as described below.
  • an optical functional layer is formed, thereby containing VO 2 particles having a preferred number average particle size of primary particles and secondary particles having a number average particle size of less than 150 nm.
  • An optical functional layer can be formed.
  • particles such as fine TiO 2 that becomes the core of particle growth are added as nucleus particles, and the VO 2 particles are produced by growing the nucleus particles. You can also.
  • the VO 2 particles are separated without drying the VO 2 particles in the aqueous dispersion. It is preferable to prepare a coating solution for forming an optical functional layer by mixing with a water-soluble binder resin solution in a dispersed state.
  • a coating solution for forming an optical functional layer by mixing with a water-soluble binder resin solution in a dispersed state.
  • 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).
  • the solution (A) may be an aqueous solution in which the substance (I) is dissolved in water, or may be a suspension in which the substance (I) is dispersed in water.
  • Examples of the substance (I) include vanadium pentoxide (V 2 O 5 ), ammonium vanadate (NH 4 VO 3 ), vanadium trichloride oxide (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 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 particles containing vanadium dioxide (VO 2 ) are obtained.
  • 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. By increasing the time, the particle diameter and the like of the obtained single crystal particles can be controlled. However, if the processing time is excessively long, the energy consumption increases.
  • the surface of the obtained vanadium dioxide particles may be subjected to a coating treatment or a surface modification treatment with a resin. Thereby, the surface of the vanadium dioxide particles is protected, and surface-modified single crystal fine particles can be obtained.
  • the surface of the vanadium dioxide particles is coated with the binder resin according to the present invention having a glass transition temperature of 65 ° C. or lower.
  • the “coating” referred to in the present invention may be a state where the entire surface of the particle is completely covered with the resin with respect to the vanadium dioxide particles, or a part of the particle surface is covered with the resin. It may be in a state.
  • a state where 50% or more of the total area of the particle surface is covered is good, and a state where 80% or more is covered is more preferable.
  • a dispersion liquid containing VO 2 -containing single crystal particles having thermochromic properties is obtained.
  • VO 2 grinding method There are various methods for making VO 2 into fine particles, but there are various methods such as bead milling, ultrasonic crushing, and high-pressure homogenizer, and any method can be used to produce VO 2 particles.
  • Various beads can be used in the bead mill, but zirconia beads are preferably used from the viewpoint of hardness and price.
  • the dispersion of vanadium dioxide particles prepared by the above-described aqueous synthesis method contains impurities such as residues generated during the synthesis process, which triggers the generation of secondary aggregated particles when forming the optical functional layer.
  • the optical functional layer may be a cause of deterioration during long-term storage, and it is preferable to remove impurities at the stage of the dispersion.
  • a method for removing impurities in the aqueous dispersion of vanadium dioxide particles conventionally known means for separating foreign substances and impurities can be applied.
  • the VO 2 particle aqueous dispersion is subjected to centrifugal separation to obtain vanadium dioxide particles. It is possible to remove the impurities in the supernatant, add and disperse the dispersion medium again, or remove the impurities out of the system using an exchange membrane such as an ultrafiltration membrane. From the viewpoint of preventing aggregation of particles, a method using an ultrafiltration membrane is most preferable.
  • the material for the ultrafiltration membrane include cellulose, polyethersulfone, and polytetrafluoroethylene (abbreviation: PTFE). Among these, polyethersulfone and PTFE are preferably used.
  • thermochromic film layer structure The typical structural example of the thermochromic film of this invention is demonstrated using a figure.
  • One of the preferable aspects of the thermochromic film of this invention is the structure by which the optical function layer is formed on the transparent base material.
  • FIG. 1 is a schematic cross-sectional view showing an example of a basic configuration of a thermochromic film having an optical functional layer containing vanadium dioxide particles and a binder resin defined in the present invention.
  • thermochromic film 1 shown in FIG. 1 has a configuration in which an optical functional layer 3 is laminated on a transparent substrate 2.
  • This optical functional layer 3 is present in a state where vanadium dioxide particles are dispersed in the binder resin B1 contained in the optical functional layer.
  • This is vanadium dioxide particles constitute the primary particles VO S of vanadium dioxide vanadium dioxide particles are present independently, an aggregate of two or more vanadium dioxide particles (also referred to as aggregates.), secondary particles VO M of VO 2 is present.
  • an aggregate of two or more vanadium dioxide particles is collectively referred to as secondary particles, and is also referred to as secondary particle aggregates or secondary aggregate particles.
  • thermochromic film of the present invention has a water content of 0.5 to 5.0 g as measured by the Karl Fischer method (JIS K 0068-2001) after standing at 80 ° C. and 80% humidity for 24 hours. / M 2 and the thickness of the optical functional layer is in the range of 0.5 to 5.0 ⁇ m.
  • the film thickness is preferably in the range of 1.0 to 3.0 ⁇ m.
  • the water content is preferably in the range of 0.6 to 2.0 g / m 2 , more preferably in the range of 0.7 to 1.0 g / m 2 .
  • the water content can be adjusted by the film thickness of the optical functional layer and the binder resin or hardener contained in the optical functional layer.
  • the moisture content can be measured by the Karl Fischer method (JIS K 0068-2001), for example, using a Karl Fischer moisture measuring device CA-31 manufactured by Mitsubishi Chemical.
  • thermochromic film having a film thickness within the above range of the optical functional layer easily breaks when the moisture content is less than 0.5 g / m 2 , and when the moisture content exceeds 5.0 g / m 2 , the reduction of vanadium dioxide proceeds. Too much. Therefore, the optical functional layer of the thermochromic film of the present invention has a film thickness and moisture content within the range, so that the film can be made flexible and the reduction of the vanadium dioxide contained can be advanced to the optimum range. Therefore, it is possible to achieve both excellent thermochromic properties and durability.
  • the number average particle diameter measured by the total particles of the primary particles VO S and secondary particles VO M of VO 2 particles in the optical functional layer 3, is preferably 200nm or less, and more preferably less than 150 nm.
  • the number average particle diameter of the VO 2 particles in the optical functional layer can be determined according to the following method. First, the side surface of the optical functional layer containing vanadium dioxide particles is trimmed using a microtome or the like to expose the cross section of the optical functional layer as shown in FIG. Next, the exposed cross section is photographed at a magnification of 10,000 to 100,000 times using a transmission electron microscope (TEM). The particle diameter is measured for all vanadium dioxide particles present in a certain area of the photographed cross section.
  • TEM transmission electron microscope
  • the vanadium dioxide particles to be measured are preferably in the range of 50 to 300 particles.
  • the photographed vanadium dioxide particle group primary particles and secondary particles are mixed as shown in FIG. 1, and the particle diameter of the primary particles of vanadium dioxide is the diameter of each independent particle. If it is not spherical, the projected area of the particle is converted into a circle, and the diameter is taken as the particle diameter.
  • the secondary particles of vanadium dioxide in which two or more particles are aggregated after obtaining the projected area of the whole aggregate, the projected area is converted into a circle, and the diameter is used as the The aggregated secondary particles are defined as one particle.
  • the number average diameter is obtained for each diameter of the primary particles and secondary particles obtained as described above. Since the cut-out cross-sectional portion has a variation in particle distribution, the measurement of the number-average diameter is carried out for 10 cross-sectional areas of different scenes, the total number-average diameter is obtained, and the number-average particle referred to in the present invention The diameter.
  • thermochromic film of the present invention may have a near-infrared light shielding layer having a function of shielding at least part of light within a wavelength range of 700 to 1000 nm, in addition to the optical functional layer.
  • the visible light transmittance measured by JIS R 3106-1998 is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more. It is.
  • thermochromic film ⁇ Each component of thermochromic film>
  • the optical functional layer which is a constituent element of the thermochromic film of the present invention, a resin base material provided if necessary, and the near infrared light shielding layer will be described.
  • the optical functional layer used in the present invention contains at least vanadium dioxide particles exhibiting thermochromic properties and a resin binder.
  • the vanadium dioxide particles exhibiting thermochromic properties are as described above, and the resin binder has a reactive functional group and is water-soluble.
  • the resin binder according to the present invention is also referred to as “water-soluble binder resin having a reactive functional group”.
  • the binder resin used in the optical functional layer according to the present invention has a reactive functional group and is water-soluble (water-soluble binder resin having a reactive functional group).
  • the water solubility of the binder resin here means the temperature at which the water-soluble resin is most dissolved, and when it is dissolved in water at a concentration of 0.5% by mass, it is filtered through a G2 glass filter (maximum pores 40 to 50 ⁇ m). In this case, the mass of the insoluble matter separated by filtration is within 50% by mass of the added water-soluble resin.
  • the reactive functional group include a hydroxy group, a methoxy group, a hydroxypropoxy group, an acetoacetyl group, a carbonyl group, and a carboxy group.
  • water-soluble resin having a reactive functional group examples include polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer.
  • Acrylic resins such as vinyl acetate-acrylic acid ester copolymer or acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid Styrene acrylic resin such as ester copolymer, styrene- ⁇ -methylstyrene-acrylic acid copolymer, or styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-sodium styrenesulfonate copolymer Coalescence, styrene-2-hydroxyl Tyl acrylate copolymer, styrene-2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer, st
  • the water-soluble cellulose resin that can be used for forming the optical functional layer according to the present invention is a water-soluble cellulose derivative, for example, carboxymethyl cellulose (cellulose carboxymethyl ether), methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, Examples thereof include water-soluble cellulose derivatives such as hydroxypropylmethylcellulose, carboxymethyl cellulose (cellulose carboxymethyl ether) and carboxyethyl cellulose which are carboxylic acid group-containing cellulose resins. Other examples include cellulose derivatives such as nitrocellulose, cellulose acetate propionate, cellulose acetate, and cellulose sulfate.
  • the water-soluble binder resin having a reactive functional group is a resin containing 50 mol% or more of repeating units having a hydroxy group.
  • the repeating unit component originally has three hydroxy groups, and a part of the three hydroxy groups is substituted.
  • Constaining 50 mol% or more of a repeating unit component having a hydroxy group means that 50 mol% or more of the repeating unit component having a hydroxy group in this substituent or a repeating unit component in which one or more unsubstituted hydroxy groups remain is contained. Represents.
  • the hardener used in the present invention is not particularly limited as long as it causes a curing reaction with the binder resin.
  • boric acid an isocyanate compound, a melamine compound, a carbodiimide compound, an epoxy compound, or the like can be used.
  • the isocyanate compound include compounds having an isocyanate group such as tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI).
  • Examples of the melamine compound include MX-706 manufactured by Sanwa Chemical Co., Ltd., becamine manufactured by DIC Co., Ltd., Watersol, and Nicaridine manufactured by Nippon Carbide Industries Co., Ltd.
  • carbodiimide compounds there are carbodilites manufactured by Nisshinbo Chemical Co., Ltd., and epoxy compounds such as Denasel manufactured by Nagase ChemteX Co., Ltd. and Epolite manufactured by Kyoeisha Chemical Co., Ltd.
  • the additive concentration ranges from 1 to 50% by mass with respect to the resin.
  • the inside is preferable. Two or more kinds of the above hardeners may be used in combination.
  • optical additives for optical functional layers Various additives that can be applied to the optical functional layer used in the present invention as long as the effects of the present invention are not impaired are listed below.
  • surfactants such as cation or nonion, JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-242871, and JP-A-4-242 209266, etc.
  • optical brighteners sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate and other pH adjusters
  • antifoaming agents Lubricants such as diethylene glycol, antiseptics, antifungal agents, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, viscosity reducing agents, lubricants, infrared absorbers
  • additives such as dyes and pigments.
  • the 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 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 provide 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 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, for example, when producing a laminated glass, Followability to the curved glass surface is improved.
  • the transparent substrate 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.
  • the transparent substrate preferably has a thermal shrinkage rate in the range of 0.1 to 3.0% at a temperature of 150 ° C., The content is more preferably in the range of 1.5 to 3.0%, and further preferably in the range of 1.9 to 2.7%.
  • the transparent substrate applicable to the thermochromic 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, polyethylene, polypropylene, etc.
  • Polyester films for example, polyethylene terephthalate, polyethylene naphthalate, etc.
  • polyvinyl chloride for example, polyethylene terephthalate, polyethylene naphthalate, etc.
  • polyvinyl chloride for example, polyethylene terephthalate, polyethylene naphthalate, etc.
  • triacetyl cellulose films and the like, preferably polyester films and triacetyl cellulose films.
  • the polyester film (hereinafter simply referred to as “polyester”) is not particularly limited, but is preferably a polyester having a film-forming property having a dicarboxylic acid component and a diol component as main components.
  • the main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid.
  • diol component examples include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.
  • polyesters having these as main components from the viewpoints of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred.
  • polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.
  • particles When using a transparent resin film as a transparent substrate, in order to facilitate handling, particles may be included within a range that does not impair transparency.
  • particles used in the present invention include inorganic particles such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and crosslinked polymers. Examples thereof include organic particles such as particles and calcium oxalate.
  • the method of adding particles include a method of adding particles in a polyester as a raw material, a method of adding directly to an extruder, and the like. Well, you may use two methods together.
  • additives may be added in addition to the above particles as necessary. Examples of such additives include stabilizers, lubricants, cross-linking agents, anti-blocking agents, antioxidants, dyes, pigments, and ultraviolet absorbers.
  • the transparent resin film may be subjected to relaxation treatment or off-line heat treatment in terms of dimensional stability.
  • the relaxation treatment is preferably carried out in the process from the heat setting in the stretching process of the polyester film to the winding in the transversely stretched tenter or after exiting the tenter.
  • the relaxation treatment is preferably performed at a treatment temperature in the range of 80 to 200 ° C., more preferably the treatment temperature is in the range of 100 to 180 ° C.
  • the relaxation rate is preferably within a range of 0.1 to 10% in both the longitudinal direction and the width direction, and more preferably, the relaxation rate is within a range of 2 to 6%.
  • the relaxed substrate is subjected to off-line heat treatment to improve heat resistance and to improve dimensional stability.
  • the transparent resin film is preferably coated with the undercoat layer coating solution in-line on one or both sides during the film formation process. In the present invention, undercoating during the film forming process is referred to as in-line undercoating.
  • thermochromic film of the present invention in addition to the optical functional layer, a near infrared light shielding layer having a function of shielding at least part of the light wavelength range within the range of 700 to 1000 nm may be provided.
  • a near infrared light shielding layer having a function of shielding at least part of the light wavelength range within the range of 700 to 1000 nm.
  • JP 2012-131130 A, JP 2012-139948 A, JP 2012-185342 A, JP 2013-080178 A Reference can be made to constituent elements and formation methods described in JP-A-2014-089347.
  • thermochromic film of this invention it can be used as a thermochromic composite body provided with the thermochromic film as a component.
  • a laminated glass can be constituted by being sandwiched between a pair of glass constituent members, and this laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. Laminated glass can be used for other purposes.
  • the laminated glass is preferably laminated glass for buildings or vehicles.
  • the laminated glass can be used for an automobile windshield, side glass, rear glass, roof glass, or the like.
  • 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.
  • inorganic glass is preferred from the viewpoint of safety when it is damaged by an external impact.
  • the present invention can also be applied to other than glass, and can be a composite composed of a thermochromic film support including glass and a thermochromic.
  • thermochromic film represents a thermochromic film
  • composite represents a thermochromic complex
  • Water content represents the water content of the optical functional layer.
  • the total thickness of the heat shielding layer and the variable property layer was defined as the thickness of the optical functional layer.
  • thermochromic film 9 g of an aqueous dispersion of vanadium dioxide particles (15% by mass) having a primary particle diameter of 55 nm and 91 g of 5% by mass of polyvinyl alcohol (PVA-124; polymerization degree: 2400, saponification degree: 98 to 99 mol%, manufactured by Kuraray Co., Ltd.) And the coating liquid which mixed 9.1 g of boric acid (5 mass%) as a hardening agent was produced. Next, the coating solution was applied onto a PET film having a thickness of 50 ⁇ m so that the film thickness of the optical functional layer was 1.5 ⁇ m, and dried with hot air at 110 ° C. for 2 minutes to produce a film 101.
  • PVA-124 polymerization degree: 2400, saponification degree: 98 to 99 mol%, manufactured by Kuraray Co., Ltd.
  • the films 102 to 133 were produced in the same manner as the film 101 except that the materials were changed according to Table 1.
  • Table 1 MC represents 5 mass% methylcellulose, and Shin-Etsu Chemical Co., Ltd. product was used.
  • HEC represents 5 mass% hydroxyethyl cellulose, and Shin-Etsu Chemical Co., Ltd. product was used.
  • HPMC represents 5% by mass hydroxypropyl methylcellulose, and one manufactured by Shin-Etsu Chemical Co., Ltd. was used.
  • PL represents a polyester resin, and “EASTER” Copolyester 6763 manufactured by Eastman Chemical Co. was used.
  • FP represents a 65% by mass TFE-based curable functional group-containing fluororesin solution, and Zaffle GK570 manufactured by Daikin Industries, Ltd. was used.
  • the types of hardeners are: A: boric acid (manufactured by Kanto Chemical Co., Inc.), B: hexamethylene diisocyanate (manufactured by Asahi Kasei Chemicals Corporation, Duranate (registered trademark) WT30-100), C: polyisocyanate (DIC) Beccamin (registered trademark) M-3), E: aqueous melamine resin (Watersol (registered trademark) S-695 manufactured by DIC Corporation), F: carbodiimide (Carbodilite (registered trademark) manufactured by Nisshinbo Chemical Co., Ltd.) SW-126), G: Epoxy (Nagase ChemteX Corporation Denacol (registered trademark) EX-810), H: Polyisocyanate (Sumika Bayer Urethane Co.
  • a film (optical functional layer) 135 was obtained in the same manner as the film 134 except that the molybdenum-doped vanadium dioxide was changed to 23 parts, and the polyester resin “EASTER” Copolyester 6763 (manufactured by Eastman Chemical) was changed to 77 parts.
  • thermochromic pigment Black TCA1015 manufactured by Sands Co., Ltd.
  • Zeffle GK570 Zeffle GK570
  • N3300 curing agent
  • thermochromic films 101 to 136 produced as described above.
  • the measuring method of water content is as follows.
  • thermochromic films 101 to 136 using a bending tester type 1 (manufactured by Imoto Seisakusho, model IMC-AOF2, mandrel diameter ⁇ 20 mm) based on a bending test method based on JIS K5600-5-1: 1999. Bending tests were performed. The surface of the thermochromic film after the bending test was visually observed, and the flexibility was evaluated according to the following criteria.
  • thermochromic film ⁇ No folding marks or cracks are observed on the surface of the thermochromic film ⁇ : Some bending marks are observed on the surface of the thermochromic film ⁇ : Slight cracks are observed on the surface of the thermochromic film ⁇ : Thermochromic film There are many obvious cracks on the surface.
  • thermochromic complex Each of the produced thermochromic films 101 to 136 is made into a transparent adhesive sheet (manufactured by Nitto Denko Corporation) with a size of 15 cm ⁇ 20 cm of a glass plate having a thickness of 1.3 mm (manufactured by Matsunami Glass Kogyo Co., Ltd., “sliding glass white edge polishing”).
  • thermochromic composites 201 to 236 produced by bonding LUCIACS CS9621T was evaluated.
  • thermochromic evaluation Using the produced thermochromic composites 201 to 236, the following heat resistance in the summer and winter conditions was evaluated, and the thermochromic properties of the thermochromic film were determined.
  • thermochromic complex was placed on the wall of the environmental test chamber at room temperature of 28 ° C. Specifically, an environmental test room was used assuming that the indoor side of the environmental test room is a thermochromic film and the side adjacent to the wall surface is glass, assuming a Japanese cool biz room. A 150 W halogen lamp that assumed the summer sun was lit from a position 50 cm away from the wall surface of the part where the thermochromic complex was placed in the environmental test room. Further, assuming that the thermochromic complex is heated by the accumulation of sunlight irradiation, the thermochromic complex was heated to 70 ° C. with a thermocouple.
  • thermometer was installed at a position 1 m away from the thermochromic complex in the environmental test chamber, the temperature after 1 hour was measured under the above conditions, and the evaluation performed according to the following criteria was evaluated as “before wet heat resistance”. .
  • a thermometer was installed at a position 1 m away from the thermochromic complex in the environmental test chamber, as in the evaluation before the wet heat resistance. The temperature after 1 hour was measured, and the evaluation performed according to the following criteria was evaluated as “after wet heat resistance”.
  • Temperature after 1 hour is less than 29 ° C, almost no temperature rise due to external light
  • Temperature after 29 hours is 29 °C or more and less than 32 °C ⁇ ⁇ : After 1 hour The temperature is 32 ° C. or more and less than 34 ° C.
  • ⁇ The temperature after the passage of 1 hour is 34 ° C. or more and less than 36 ° C.
  • ⁇ The temperature after the passage of 1 hour is 36 ° C. or more, which is a harsh environment.
  • thermochromic composite was placed on the wall of an environmental test room having a room temperature of 20 ° C. Specifically, an environmental test chamber was used assuming that the indoor side of the environmental test room is a thermochromic film and the side adjacent to the wall surface is glass, assuming a Japanese warm biz room. From a position 50 cm away from the wall surface of the part where the thermochromic complex was placed in the environmental test room, a 100 W halogen lamp was used that assumed the winter sun.
  • thermometer was installed at a position 1 m away from the thermochromic complex in the environmental test chamber, the temperature after 1 hour was measured under the above conditions, and the evaluation performed according to the following criteria was evaluated as “before wet heat resistance”. .
  • a thermometer was installed at a position 1 m away from the thermochromic complex in the environmental test chamber, as in the evaluation before the wet heat resistance. The temperature after 1 hour was measured, and the evaluation performed according to the following criteria was evaluated as “after wet heat resistance”.
  • ⁇ Temperature after 1 hour is 26 ° C or higher, and heat energy from external light has entered moderately.
  • ⁇ Temperature after 24 hours is more than 24 ° C and less than 26 ° C. Later temperature is 22 ° C. or more and less than 24 ° C.
  • ⁇ Temperature after 21 hours is 21 ° C. or more and less than 22 ° C.
  • ⁇ Many near infrared light is unconditionally shielded and after 1 hour The temperature is less than 21 ° C
  • Haze is less than 2.0% ⁇ : Haze is 2.0% or more and less than 3.0% ⁇ ⁇ : Haze is 3.0% or more and less than 5.0% ⁇ : Haze 5.0% or more and less than 8.0% x: Haze is 8.0% or more
  • thermochromic film of the present invention As can be seen from the results in Table 2, it was found that the flexibility, wet heat resistance, and haze when using the thermochromic film of the present invention were superior to those when using the thermochromic film of the comparative example.
  • thermochromic film and a thermochromic composite containing vanadium dioxide particles exhibiting excellent thermochromic properties and durability can be obtained, and these can be suitably used for near infrared light shielding films and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

Le problème de la présente invention concerne un film thermochrome et un composite thermochrome qui comprennent des particules de dioxyde de vanadium présentant d'excellentes propriétés thermochromes et une excellente durabilité. Ce film thermochrome présente, sur un substrat transparent, une couche optiquement fonctionnelle qui comprend au moins des particules de dioxyde de vanadium dotées de propriétés thermochromes et une résine de liant. Le film thermochrome est caractérisé en ce que : la résine de liant présente un groupe fonctionnel réactif et est soluble dans l'eau; la teneur en eau de la couche optiquement fonctionnelle après avoir été laissée au repos à 80°C et à une humidité de 80% pendant 24 heures se situe dans la plage de 0,5 à 5,0 g/m2 ; et l'épaisseur de la couche optiquement fonctionnelle se situe dans la plage de 0,5 à 5,0 µm.
PCT/JP2016/067606 2015-08-21 2016-06-14 Film thermochrome et composite thermochrome WO2017033533A1 (fr)

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WO2024122611A1 (fr) * 2022-12-07 2024-06-13 国立研究開発法人産業技術総合研究所 Matériau électrochromique noir et son procédé de fabrication, peinture et son procédé de fabrication, peinture mélangée et leur procédé de fabrication, électrode à couleur variable et son procédé de fabrication, et élément électrochromique

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WO2024122611A1 (fr) * 2022-12-07 2024-06-13 国立研究開発法人産業技術総合研究所 Matériau électrochromique noir et son procédé de fabrication, peinture et son procédé de fabrication, peinture mélangée et leur procédé de fabrication, électrode à couleur variable et son procédé de fabrication, et élément électrochromique

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