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WO2017077797A1 - Film thermochromique et corps composite thermochromique - Google Patents

Film thermochromique et corps composite thermochromique Download PDF

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Publication number
WO2017077797A1
WO2017077797A1 PCT/JP2016/079224 JP2016079224W WO2017077797A1 WO 2017077797 A1 WO2017077797 A1 WO 2017077797A1 JP 2016079224 W JP2016079224 W JP 2016079224W WO 2017077797 A1 WO2017077797 A1 WO 2017077797A1
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WIPO (PCT)
Prior art keywords
thermochromic
film
particles
vanadium dioxide
layer
Prior art date
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Ceased
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PCT/JP2016/079224
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English (en)
Japanese (ja)
Inventor
丈範 熊谷
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to CN201680064232.0A priority Critical patent/CN108351445B/zh
Priority to JP2017548676A priority patent/JP6747450B2/ja
Publication of WO2017077797A1 publication Critical patent/WO2017077797A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides

Definitions

  • the present invention relates to a thermochromic film and a thermochromic composite, and more particularly to a thermochromic film that exhibits durability and stability of haze.
  • 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.
  • a near infrared light shielding film an optical film containing a conductor such as ITO (indium tin oxide) as an infrared absorbing substance is disclosed.
  • Patent Document 1 discloses a near infrared light shielding film including a functional plastic film having an infrared reflection layer and an infrared absorption layer.
  • Patent Document 2 has a reflection layer laminate in which a large number of low refractive index layers and high refractive index layers are alternately laminated, and by adjusting the thickness of each refractive index layer, near infrared light can be obtained.
  • a near-infrared light shielding film that selectively reflects light has been proposed.
  • the near-infrared light shielding film having such a configuration is preferably used in a low-latitude zone near the equator where the illuminance of sunlight is high due to its high near-infrared light shielding effect.
  • a thermochromic material that is controlled by the above 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 about 50 to 60 ° C. and exhibit thermochromic properties.
  • Patent Document 3 reports that VO 2 is protected with a silane coupling agent and a long-chain alkyl resin. Moreover, in patent document 4, although it is reported protecting by polycarboxylic acid, nothing is reported regarding the haze fluctuation
  • JP 2010-222233 A International Publication No. 2013/065679 Special table 2015-513508 gazette JP 2012-25629 A
  • the present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is to provide a thermochromic film and a thermochromic composite that have both durability and stability of haze.
  • the present inventor has added a chelate complex to a vanadium dioxide-containing layer (thermochromic layer), thereby causing haze problems caused by changes in particle shape and alkali extracted from glass. It turned out that the influence of an ingredient can be suppressed. That is, the said subject of this invention is solved by the following means.
  • thermochromic film containing vanadium dioxide particles exhibiting thermochromic properties
  • thermochromic film comprising a vanadium dioxide-containing layer containing a chelate complex together with the vanadium dioxide particles.
  • thermochromic film according to item 1 wherein the content of the chelate complex is in the range of 0.1 to 20% by mass with respect to the total mass of the vanadium dioxide-containing layer.
  • thermochromic film according to item 2 wherein the content of the chelate complex is in the range of 1 to 15% by mass with respect to the total mass of the vanadium dioxide-containing layer.
  • thermochromic composite comprising a thermochromic film according to any one of items 1 to 3 bonded to glass.
  • thermochromic composite according to item 4 which is a composite in which a thermochromic film having an adhesive layer adjacent to the vanadium dioxide-containing layer is bonded to the glass.
  • thermochromic film and a thermochromic composite that have both durability and stability of haze.
  • thermochromic film of the present invention Schematic sectional view of the thermochromic film of the present invention Schematic sectional view of the thermochromic film of the present invention Schematic sectional view of the thermochromic complex of the present invention Schematic sectional view of thermochromic composites of Comparative Example 2 and Comparative Example 3 Transmission electron micrograph of thermochromic film of comparative example Transmission electron micrograph of thermochromic film of comparative example Transmission electron micrograph of the thermochromic film of the present invention Transmission electron micrograph of the thermochromic film of the present invention
  • thermochromic film of the present invention is a thermochromic film containing vanadium dioxide particles exhibiting thermochromic properties, and has a vanadium dioxide-containing layer containing a chelate complex together with the vanadium dioxide particles. This feature is a technical feature common to or corresponding to the claimed invention.
  • the content of the chelate complex is within the range of 0.1 to 20% by mass with respect to the total mass of the vanadium dioxide-containing layer, so that the influence of moisture and oxygen from the outside can be more effectively achieved. It is preferable from the viewpoint of suppression.
  • the content of the chelate complex is in the range of 1 to 15% by mass with respect to the total mass of the vanadium dioxide-containing layer from the viewpoint of manifesting the effects of the present invention.
  • thermochromic composite of the present invention is preferable because it is a composite in which the thermochromic film of the present invention is bonded to glass, so that the glass can be used as a support in various fields for construction and vehicles.
  • thermochromic film having an adhesive layer adjacent to the vanadium dioxide-containing layer is bonded to the glass is preferable 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.
  • thermochromic film of the present invention is a thermochromic film containing vanadium dioxide particles exhibiting thermochromic properties, and has a vanadium dioxide-containing layer containing a chelate complex together with the vanadium dioxide particles.
  • the thermochromic property refers to a property of controlling the optical properties of shielding or transmitting near infrared light by temperature.
  • the thermochromic property exhibited by the vanadium dioxide particles according to the present invention (hereinafter also simply referred to as “VO 2 particles”) is particularly if the optical properties such as light transmittance and light reflectance change reversibly due to temperature changes. It is not limited.
  • the preferable thermochromic property exhibited by the vanadium dioxide particles according to the present invention is, for example, a difference in light transmittance at 25 ° C./50% RH and 85 ° C./85% RH of 7% or more, more preferably 10% or more. Furthermore, it is 15% or more.
  • the light transmittance can be measured as the light transmittance at a wavelength of 1500 nm using, for example, a spectrophotometer V-670 (manufactured by JASCO Corporation).
  • the vanadium dioxide particles showing the thermochromic property of the present invention will be described, and details of vanadium dioxide particles, chelate complexes and other materials used for the thermochromic film will be described.
  • 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 according to 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 other compounds such as VO 2 particles of other crystal types such as A-type or B-type, organic compounds, and other metal oxides as long as the purpose is not impaired. Good.
  • the VO 2 particles according to the present invention are present in a vanadium dioxide-containing layer (hereinafter also referred to as a thermochromic layer) in a state where the number average particle diameters of the primary particles and the secondary particles are less than 500 nm.
  • a thermochromic layer in a state where the number average particle diameters of the primary particles and the secondary particles are less than 500 nm.
  • 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 less than 500 nm, more preferably 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.
  • 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.
  • It may contain at least one selected element. By adding such an element, it becomes possible to control the phase transition characteristics (particularly the dimming temperature) of the vanadium dioxide particles.
  • the total amount of such additives with respect to the finally obtained vanadium dioxide particles is sufficient to be about 0.1 to 5.0 atomic% with respect to the vanadium (V) atom.
  • the amount of the dispersant added is preferably in the range of 0.1 to 1.0% by mass.
  • water-based dispersants in addition to low molecular weight dispersants such as alkyl sulfonates, alkyl benzene sulfonates, diethylamine, ethylenediamine, quaternary ammonium salts, polyoxyethylene nonylphenyl ether, polyexethylene lauryl Acid ether, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyethylene glycol, silane coupling agent and the like can be mentioned, and in particular, polyvinyl pyrrolidone or cellulose resin is preferable, and it can be used in combination with the chelate complex in the present invention.
  • thermochromic layer As the organic solvent-based dispersant, commonly used organic dispersants such as alkylamines, silane coupling agents, and phosphoric acid-based dispersants can be used. Then, without drying the VO 2 particles in the dispersion With these dispersants can be prepared thermochromic layer forming coating solution as described below. By using the coating liquid for forming a thermochromic layer in this state, a thermochromic 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. A thermochromic layer can be formed.
  • VO 2 particles if necessary, 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.
  • water-soluble binder resin as binder resin
  • 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 a thermochromic 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.
  • 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 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).
  • the thermochromic properties of the vanadium dioxide particles in particular, the transition temperature can be controlled.
  • 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 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. Preferably, 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 water-based synthesis method contains impurities such as residues generated during the synthesis process, which triggers the generation of secondary aggregated particles when forming the thermochromic layer. Further, it may become a deterioration factor in long-term storage of the thermochromic layer, and it is preferable to remove impurities at the stage of the dispersion.
  • 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.
  • the chelate complex according to the present invention refers to a metal complex in which at least one ligand having a plurality of coordination sites is coordinated to a metal ion.
  • the metal complex is a compound having a metal atom in the molecular structure and a ligand bonded to the metal atom through a coordinate bond.
  • Chelating ligands include EDTA (ethylenediaminetetraacetic acid), EDA (ethylenediamine), BAPTA (1,2-bis (o-aminophenoxide) ethane-N, N, N ′, N′-tetraacetic acid) and crown ether (12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, diaza-18-crown-6) and the like can be used, but are not limited thereto.
  • Examples of the structure are preferably aluminum trisacetylacetonate, diisopropoxybis (acetylacetonato) titanium, zirconium tetraacetylacetonate and the like, but are not limited thereto.
  • chelate complex commercially available products may be used, such as titanium dipropoxy diacetylacetonate (Matsumoto Fine Chemical Co., Ltd., Olga Chicks TC-100: trade name), titanium triethanolaminate (Matsumoto Fine Chemical Co., Ltd., Olga Tix).
  • TC-400 trade name
  • titanium dioctoxy dioctylene glycolate Matsumoto Fine Chemical Co., Ltd., Olgatyx TC-200: trade name
  • titanium diporopoxydiethyl acetate Matsumoto Fine Chemical Co., Ltd., Olgatechs TC-) 750: Trade name
  • Titanium 2- (2-aminoethylamino) ethoxide Matsumoto Fine Chemicals Co., Ltd., Olgatyx TC-510: Trade name
  • Hydroxyzirconium tris (ammonium lactate) (Matsumo) Fine Chemicals Co., Ltd., Orgatix ZC-300: trade name) zirconium monoacetylacetonate (Matsumoto Fine Chemical Co., Orgatix ZC-540: trade name) and the like as commercial products.
  • the content of the chelate complex is preferably in the range of 0.1 to 20% by mass, and more preferably in the range of 1 to 15% by mass with respect to the total mass of the vanadium dioxide-containing layer.
  • thermochromic film The typical structural example of the thermochromic film of this invention is demonstrated with reference to figures.
  • One of the preferable embodiments of the thermochromic film of the present invention is a configuration in which a vanadium dioxide-containing layer (thermochromic layer) is formed on a transparent substrate.
  • FIG. 1 is a schematic cross-sectional view showing an example of a basic configuration of a thermochromic film having a thermochromic 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 a thermochromic layer 3 is laminated on a transparent substrate 2.
  • the thermochromic layer 3 is present in a state where vanadium dioxide particles are dispersed in the binder resin B1 contained in the thermochromic 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 called aggregates), VO 2 of secondary particles VO M 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.
  • 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 thermochromic layer 3 is preferably less than 150 nm.
  • the number average particle diameter of the VO 2 particles in the thermochromic layer can be determined according to the following method.
  • Another preferred embodiment of the thermochromic film of the present invention has a hybrid configuration in which the thermochromic layer also serves as a transparent substrate.
  • FIG. 2 is a schematic sectional view showing another example of the basic configuration of the thermochromic film of the present invention, in which the transparent substrate 2 and the thermochromic layer 3 shown in FIG. 1 are composed of the same layer.
  • the resin constituting the thermochromic layer (2 + 3) and constituting the transparent substrate the binder resin B2 contained in the thermochromic layer is used, and the VO 2 particles are contained in the binder resin B2 in the VO 2.
  • a primary particle VO S of, being the secondary particles VO M of vanadium dioxide particles dispersed, is formed to have constituted a thermochromic layer having both a transparent substrate in a single layer.
  • the thermochromic film of the present invention may have a near infrared light shielding layer 4 having a function of shielding at least part of light within a wavelength range of 700 to 1000 nm.
  • the visible light transmittance measured by JIS R3106-1998 is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more. is there.
  • thermochromic layer which is a component of the thermochromic film of this invention, the transparent base material provided as needed, and the detail of a near-infrared-light shielding layer are demonstrated.
  • thermochromic layer used in the present invention preferably contains at least VO 2 particles and a resin binder.
  • binder resin applicable to the present invention include a water-soluble binder resin and a solvent-based binder, and are not particularly limited, but among them, a water-soluble binder resin is preferable.
  • a water-soluble binder resin can also be used as the binder resin.
  • the water-soluble binder resin here is a resin that dissolves or disperses 1.0 g or more with respect to 100 g of water at 25 ° C.
  • a resin that is dissolved in hot water and similarly dissolved at 25 ° C. is also defined as a water-soluble binder resin in the present invention.
  • thermochromic layer examples include gelatins, graft polymers of gelatin and other polymers, proteins such as albumin and casein, celluloses, sodium alginate, cellulose sulfate, dextrin, Naturally derived materials such as sugar derivatives such as dextran and dextran sulfate, thickening polysaccharides, polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer
  • Acrylic resins such as polymers, vinyl acetate-acrylic acid ester copolymers, or acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic Acid Este Styrene acrylic acid resin such as copolymer, styrene
  • a polymer containing 50 mol% or more of repeating unit components having a hydroxy group which has a high affinity with VO 2 particles and has a high effect of preventing particle aggregation even during drying of film formation, is preferable.
  • examples thereof include celluloses, polyvinyl alcohols, acrylic resins having a hydroxy group, etc.
  • polyvinyl alcohols and celluloses can be most preferably used.
  • Usable crosslinking agents for obtaining water resistance of resin binders include isocyanate compounds, melamine compounds, glyoxal compounds, oxazoline compounds, aziridines, titanium chelates, urea formalin resins, glutaraldehyde, tannic acid, carbodiimide compounds Etc. can be used.
  • the addition concentration is preferably in the range of 1 to 50% by mass relative to the resin.
  • An aqueous emulsion can also be added to improve water resistance.
  • Preferable examples include acrylic resin emulsion and urethane resin emulsion.
  • thermochromic layer Various additives that can be applied to the thermochromic 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, thinning agents, lubricants, infrared absorbers
  • additives such as dyes and pigments.
  • thermochromic layer Metal for forming thermochromic layer
  • the wet coating method used for forming the thermochromic layer is not particularly limited.
  • 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 impart flexibility and suitability for production (manufacturing process suitability). From the viewpoint, a transparent resin film is preferable.
  • “Transparent” in the present invention means that the average light transmittance in the visible light region is 50% or more, preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more.
  • the thickness of the transparent substrate 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 thermochromic 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 the thermochromic composite body 6 provided with the thermochromic film as a component.
  • the thermochromic composite 6 of the present invention is obtained by bonding the thermochromic film 1 of the present invention to the glass member 5 (see FIG. 3 and FIG. 4), or sandwiching it between a pair of glass members. It is also preferable to constitute glass.
  • the thermochromic film composite of this invention has an adhesion layer adjacent to the said vanadium dioxide content layer.
  • thermochromic layer which comprises a thermochromic film
  • positioning pinched
  • the arrangement sandwiched between the transparent substrate and the glass shown in FIG. 3 is less susceptible to external influences, and the chelate complex contained in the thermochromic layer is It is considered that the haze can be improved by suppressing the influence of alkali components derived from glass.
  • laminated glass it 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.
  • Examples of the glass member include inorganic glass and organic glass (resin glazing).
  • Examples of the inorganic glass 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.
  • Examples of the organic glass (resin glazing) include a polycarbonate plate and a poly (meth) acrylic resin plate.
  • Examples of the poly (meth) acrylic resin plate include a polymethyl (meth) acrylate plate.
  • inorganic glass is preferred from the viewpoint of safety when it is damaged by an external impact.
  • alkali-free glass is more preferable. Further, it can be applied to other than glass, and it can be a composite composed of a thermochromic film support including glass and a thermochromic film.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include acrylic pressure-sensitive adhesives, silicon pressure-sensitive adhesives, urethane pressure-sensitive adhesives, polyvinyl butyral pressure-sensitive adhesives, and ethylene-vinyl acetate pressure-sensitive adhesives. Can do. Moreover, a commercial item may be sufficient and the transparent adhesive sheet LUCIACS CS9621T made from Nitto Denko can be used preferably, for example.
  • thermochromic film of the present invention When the thermochromic film of the present invention is attached to a window glass or the like, a method of applying water by spraying water on the window and attaching the adhesive layer of the thermochromic film to the wet glass surface, the so-called water application method has been repositioned and repositioned. Etc. from the viewpoint of the above. For this reason, an acrylic pressure-sensitive adhesive that has a weak adhesive force in the presence of water is preferably used.
  • the acrylic pressure-sensitive adhesive used may be either solvent-based or emulsion-based, but is preferably a solvent-based pressure-sensitive adhesive because it is easy to increase the adhesive strength and the like, and among them, those obtained by solution polymerization are preferable.
  • the raw material for producing such a solvent-based acrylic pressure-sensitive adhesive by solution polymerization include, for example, acrylic acid esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and acryl acrylate as main monomers serving as a skeleton, As a comonomer to improve cohesive strength, vinyl acetate, acrylonitrile, styrene, methyl methacrylate, etc., to further promote crosslinking, to give stable adhesive strength, and to maintain a certain level of adhesive strength even in the presence of water
  • the functional group-containing monomer include methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, and glycid
  • This adhesive layer contains additives such as stabilizers, surfactants, UV absorbers, flame retardants, antistatic agents, antioxidants, thermal stabilizers, lubricants, fillers, coloring, adhesion modifiers, etc. It can also be made.
  • additives such as stabilizers, surfactants, UV absorbers, flame retardants, antistatic agents, antioxidants, thermal stabilizers, lubricants, fillers, coloring, adhesion modifiers, etc. It can also be made.
  • an ultraviolet absorber is also effective for suppressing deterioration of the thermochromic film due to ultraviolet rays.
  • the thickness of the adhesive layer is preferably 1 to 100 ⁇ m, more preferably 3 to 50 ⁇ m. If it is 1 micrometer or more, there exists a tendency for adhesiveness to improve and sufficient adhesive force is acquired. Conversely, if the thickness is 100 ⁇ m or less, not only the transparency of the thermochromic film is improved, but also after the thermochromic film is attached to the window glass, it does not cause cohesive failure between the adhesive layers when peeled off, and adheres to the glass surface. There is a tendency that there is no remaining agent.
  • Various additives can be added to the pressure-sensitive adhesive, and preferably an ultraviolet absorber and an antioxidant can be contained.
  • thermochromic film In Table 1, the haze, light transmittance, and light transmittance change of the composite (thermochromic composite) using the thermochromic film corresponding to the film number are shown.
  • thermochromic film [Production of Film 101] (Preparation of VO 2 particle aqueous dispersion 1) 74.9 g of vanadium dioxide particles (VO 2 , manufactured by Shinsei Chemical Co., Ltd.) was mixed with 425 mL of pure water, 200 g of 300 ⁇ m zirconia beads for bead milling were used, and pulverization was performed using an Apex mill (manufactured by Kotobuki Industries). . Ammonia water was added to the pulverized particles so that the standard oxidation-reduction potential was 330 mV and the pH at 25 ° C. was 6.5 to prepare vanadium dioxide particle aqueous dispersion 1.
  • thermochromic layer forming coating solution 1 (Preparation of thermochromic layer forming coating solution 1) The following constituent materials were sequentially added, mixed and dissolved to prepare an aqueous thermochromic layer forming coating solution 1. 15% by mass of VO 2 particle aqueous dispersion 1 (solvent: water) 9.0% by mass 5% by weight of polyvinylpyrrolidone / vinyl acetate copolymer S-630 (Made by ISP JAPAN) 76.0 mass% ORGATICS TC-400 (titanium diisopropoxybis (triethanolaminate); manufactured by Matsumoto Fine Chemical Co., Ltd.) 15.0% by mass
  • thermochromic layer On a transparent substrate of a polyethylene terephthalate film (Toray U40, double-sided easy-adhesion layer) having a thickness of 50 ⁇ m, using an extrusion coater, the thermochromic layer forming coating solution 1 prepared above has a layer thickness after drying. Wet application is performed under the condition of 1.5 ⁇ m, then hot air of 110 ° C. is blown for 2 minutes to dry, a thermochromic layer is formed, and thermochromic film 1 (film 101 having the structure shown in FIG. 1 is formed. ) Was produced.
  • thermochromic film 101 was produced in the same manner as the thermochromic film 101 except that the concentration of TC-400 was changed to 20.0% by mass.
  • thermochromic film 102 was produced in the same manner as the thermochromic film 102 except that the concentration of TC-400 was 21.0% by mass.
  • thermochromic film 103 was produced in the same manner as the thermochromic film 103 except that the concentration of TC-400 was 1.0% by mass.
  • thermochromic film 104 was produced in the same manner as in the production of the thermochromic film 104 except that the concentration of TC-400 was changed to 0.1% by mass.
  • thermochromic film 101 was produced in the same manner as in the production of the thermochromic film 101 except that ORGATICS TC-510 (titanium aminoethylamino ethanolate; manufactured by Matsumoto Fine Chemical Co.) was used instead of TC-400.
  • ORGATICS TC-510 titanium aminoethylamino ethanolate; manufactured by Matsumoto Fine Chemical Co.
  • thermochromic film 104 was produced in the same manner as the thermochromic film 104 except that TC-510 was used instead of TC-400.
  • thermochromic film 105 was produced in the same manner as the thermochromic film 105 except that TC-510 was used instead of TC-400.
  • thermochromic film 109 was produced in the same manner as the thermochromic film 101 except that ZC-300 was used instead of TC-400.
  • thermochromic film 104 was produced in the same manner as the thermochromic film 104 except that ZC-300 was used instead of TC-400.
  • thermochromic film 105 was produced in the same manner as the thermochromic film 105 except that ZC-300 was used instead of TC-400.
  • thermochromic film 101 was produced in the same manner as in the production of the thermochromic film 101 except that ORGATICS ZC-540 (zirconium tributoxy monoacetylacetonate; manufactured by Matsumoto Fine Chemical Co.) was used instead of TC-400. .
  • ORGATICS ZC-540 zirconium tributoxy monoacetylacetonate; manufactured by Matsumoto Fine Chemical Co.
  • thermochromic film 113 was produced in the same manner as the thermochromic film 104 except that ZC-540 was used instead of TC-400.
  • thermochromic film 114 was produced in the same manner as the thermochromic film 105 except that ZC-540 was used instead of TC-400.
  • thermochromic film 115 was prepared in the same manner as the thermochromic film 101 except that it was prepared without adding TC-400.
  • thermochromic film 101 was prepared in the same manner except that 4.0% by mass of a titanate coupling agent (Plenact TTS (manufactured by Ajinomoto Fine Techno Co., Ltd.)) was added instead of TC-400. Was made.
  • a titanate coupling agent Plenact TTS (manufactured by Ajinomoto Fine Techno Co., Ltd.)
  • thermochromic film 1 was prepared in the same manner except that 0.5 mass% of polycarboxylic acid (Mariarim series (AFB-0561) manufactured by NOF Corporation) was added instead of TC-400. 117 films were produced. Table 1 shows the structures of the thermochromic films 101 to 117 produced as described above.
  • thermochromic films 101 to 117 produced above are formed into a transparent adhesive sheet (manufactured by Nitto Denko Corporation) in a size of 15 mm ⁇ 20 cm of a glass plate having a thickness of 1.3 mm (manufactured by Matsunami Glass Industry Co., Ltd., “Slide Glass White Edge Polish”). , LUCIACS CS9621T).
  • the VO 2 -containing layer was bonded to the adhesive surface, and the polyethylene terephthalate was bonded to the outside, and thermochromic composites 201 to 214, 217, 220, and 221 were prepared for each of the thermochromic films prepared above (FIG. 3).
  • the thermochromic composite 216 was prepared in the same manner except that the glass of the thermochromic composite 201 was changed to non-alkali glass.
  • thermochromic composite body 218 Comparative Example 2
  • a thermochromic film 115 was used to form an adhesive layer on the side opposite to the VO 2 -containing layer forming surface of the transparent substrate and bonded to glass. (See FIG. 4).
  • thermochromic composite body 219 comparativative example 3
  • Thermochromic light transmittance evaluation Using a spectrophotometer V-670 (manufactured by JASCO Corp.), the light transmittance at a wavelength of 1500 nm at 25 ° C. (room temperature) was measured for each of the produced thermochromic complexes. Moreover, the light transmittance in wavelength 1500nm in 75 degreeC (high temperature) was measured using the heating measuring apparatus. Furthermore, the light transmittance was measured before and after the elapse of 7 days at 85 ° C. and 85% RH.
  • thermochromic film was observed with a transmission electron microscope (TEM, device name: JEM-2000FX, manufacturer: JEOL Ltd.) before and after the wet heat analysis (see FIGS. 5A to 5D).
  • 5A and 5C are TEM images of the thermochromic film before wet heat
  • FIGS. 5B and 5D are TEM images of the thermochromic film after wet heat at 85 ° C. and 85% RH. From the TEM images of FIGS. 5A and 5B, it can be confirmed that the shape of the vanadium dioxide particles changes from granular to needle-like before and after wet heat.
  • thermochromic film which added the chelate complex to the vanadium dioxide content layer is shown in FIG. 5C and FIG. 5D.
  • the shape of vanadium dioxide particles before wet heat is not significantly different from the case where no chelate complex is added, but it can be seen that the formation of acicular particles after wet heat can be suppressed at 85 ° C. and 85% RH. It was.
  • thermochromic composites 217 to 221 containing no chelate complex in the comparative example have a reduced thermochromic property after the deterioration test at 85 ° C. and 85% RH.
  • the thermochromic composites 201 to 216 were found to have a small deterioration width and high durability.
  • the comparative example 1 when comparing the thermochromic composite body 217 (Comparative Example 1) and the thermochromic composite body 218 (Comparative Example 2), the comparative example 1 has a larger deterioration width after the wet heat test. Since Comparative Example 1 has a configuration in which the VO 2 -containing layer is close to glass, but Comparative Example 2 has a configuration in which the VO 2 -containing layer is formed in the outermost layer, Comparative Example 1 is less affected by moisture and oxygen. Nevertheless, the deterioration is significant. Moreover, it is thought that the transfer of the alkaline component from glass is suppressed considering that the comparative example 3 has hardly deteriorated.
  • thermochromic complex of the present invention the deterioration is suppressed even under the condition where there is a migration of the alkali component from the glass, and it is proved that the chelate complex is effective in maintaining the thermochromic property. It was found that the thermochromic film of the present invention exhibits excellent thermochromic properties.
  • thermochromic composites 201 to 216 of the present invention all have a haze change rate of 4.0% or less, and it was found that they are suitable for practical use. From the above results, it was shown that by using the method described in the present invention, a thermochromic film having both durability and stability of haze could be produced.
  • thermochromic film and a thermochromic film composite having both durability and stability of haze can be obtained, and can be suitably used for a near infrared light shielding film and the like.

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Abstract

L'objectif de la présente invention est de fournir : un film thermochromique qui atteint un bon équilibre entre la durabilité et la stabilité du trouble ; et un corps composite thermochromique. Un film thermochrome selon la présente invention contient des particules de dioxyde de vanadium ayant des propriétés thermochromiques, et est caractérisé en ce qu'il comporte une couche contenant du dioxyde de vanadium qui contient un complexe chélaté avec les particules de dioxyde de vanadium.
PCT/JP2016/079224 2015-11-06 2016-10-03 Film thermochromique et corps composite thermochromique Ceased WO2017077797A1 (fr)

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