WO2017073183A1 - Film thermochrome et procédé de production d'un film thermochrome - Google Patents

Film thermochrome et procédé de production d'un film thermochrome Download PDF

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WO2017073183A1
WO2017073183A1 PCT/JP2016/076629 JP2016076629W WO2017073183A1 WO 2017073183 A1 WO2017073183 A1 WO 2017073183A1 JP 2016076629 W JP2016076629 W JP 2016076629W WO 2017073183 A1 WO2017073183 A1 WO 2017073183A1
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vanadium dioxide
thermochromic film
thermochromic
dioxide particles
block copolymer
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PCT/JP2016/076629
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English (en)
Japanese (ja)
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保彦 高向
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コニカミノルタ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy

Definitions

  • the present invention relates to a thermochromic film and a method for producing a thermochromic film, and more particularly to a thermochromic film that exhibits excellent 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.
  • thermochromic materials that can be used are attracting attention.
  • the thermochromic material can control near-infrared light shielding and transmission optical properties by temperature, and a typical material thereof 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 described in Patent Document 1 improves the chemical stability and dispersibility of vanadium dioxide particles by organically modifying long-chain molecules on the surface of vanadium dioxide nanoparticles.
  • thermochromic film described in Patent Document 1 has a slow thermochromic response with a change in infrared transmittance, and further performance improvement is required.
  • thermochromic film exhibiting high thermochromic responsiveness while suppressing haze
  • manufacturing method for manufacturing the thermochromic film Is to provide.
  • thermochromic film of the present invention has vanadium dioxide particles exhibiting thermochromic properties and a partial structure represented by the following general formula (I) It has been found that by containing a block copolymer having a high thermochromic responsiveness while keeping the haze low, the present invention has been achieved. That is, the said subject of this invention is solved by the following means.
  • thermochromic film comprising vanadium dioxide particles exhibiting thermochromic properties and a block copolymer having a partial structure represented by the following general formula (I).
  • Formula (I) -(A) a-(B) b-(C) c- [Wherein, A, B and C each represent a repeating unit structure of a monomer constituting the block copolymer.
  • A represents a repeating unit structure of a hydrophobic unsaturated monomer selected from the group consisting of styrenes and alkylene esters.
  • B represents a repeating unit structure of a hydrophilic unsaturated monomer containing a nonionic group.
  • C represents the repeating unit structure of the adsorptive unsaturated monomer containing an amino group or a nitrogen-containing heterocyclic group.
  • a, b and c represent the constituent molar ratio (mol%) of the repeating unit structure of each monomer in the block copolymer, and the total of the constituent molar ratios of a, b and c is 100 mol%. . ]
  • thermochromic film according to item 1 wherein C represents a unit structure of 4-vinylpyridine.
  • thermochromic film according to claim 1 or 2 wherein the vanadium dioxide particles further contain an element for adjusting a phase transition temperature.
  • thermochromic film according to any one of Items 1 to 3, further comprising a hydrophobic binder.
  • thermochromic film for producing the thermochromic film according to Item 4, Mixing the powder of the vanadium dioxide particles and an organic solvent containing the block copolymer to prepare a dispersion; Mixing and applying the hydrophobic binder to the dispersion and drying;
  • a method for producing a thermochromic film comprising:
  • thermochromic film for producing the thermochromic film according to Item 4
  • Adding an aqueous solution containing the block copolymer to an aqueous dispersion in which the vanadium dioxide particles are dispersed, and preparing a mixed solution Adding an organic solvent to the mixed solution, moving the vanadium dioxide particles and the block copolymer from an aqueous phase to an organic phase, and separating and extracting the organic phase; Mixing and applying the hydrophobic binder to the organic phase and drying;
  • the manufacturing method of the thermochromic film characterized by having.
  • thermochromic film exhibiting high thermochromic responsiveness while suppressing haze, and a production method for producing the thermochromic film.
  • thermochromic film excellent in high thermochromic responsiveness, chemical stability and dispersibility accompanied by a change in infrared transmittance by allowing the surface of the vanadium dioxide particles and the block copolymer to moderately interact with each other. I guess it was possible to provide.
  • thermochromic film of the present invention Schematic sectional view showing an example of the basic configuration of the thermochromic film of the present invention
  • thermochromic film of the present invention Schematic sectional view showing another example of the basic configuration of the thermochromic film of the present invention
  • thermochromic film having a near infrared light shielding layer of the present invention Schematic sectional view showing an example of the layer arrangement of a thermochromic film having a near infrared light shielding layer of the present invention
  • thermochromic film of the present invention is characterized by containing vanadium dioxide particles exhibiting thermochromic properties and a block copolymer having a partial structure represented by the general formula (I). This feature is a technical feature common to or corresponding to the claimed invention.
  • C represents a unit structure of 4-vinylpyridine from the viewpoint of the effect of the present invention.
  • the vanadium dioxide particles further include an element for adjusting the phase transition temperature, thereby adjusting and optimizing the phase transition temperature, thereby improving the load on the cooling equipment in summer and the heating equipment in winter. It is more preferable from the point that both load can be reduced and energy saving measures can be taken.
  • a hydrophobic binder from the viewpoint of improving the compatibility with the vanadium dioxide particles and further improving the haze and thermochromic responsiveness.
  • thermochromic film for producing the thermochromic film of the present invention comprises a step of mixing a powder of the vanadium dioxide particles and an organic solvent containing the block copolymer to prepare a dispersion, And the step of mixing and applying the hydrophobic binder to the dispersion and applying / drying is preferable in that moisture can be eliminated as much as possible and haze and thermochromic responsiveness can be further improved.
  • the method for producing a thermochromic film for producing the thermochromic film of the present invention includes a step of adding an aqueous solution containing the block copolymer to an aqueous dispersion in which the vanadium dioxide particles are dispersed to prepare a mixed solution. Adding an organic solvent to the mixed solution, moving the vanadium dioxide particles and the block copolymer from an aqueous phase to an organic phase, separating and extracting the organic phase, and adding the hydrophobic binder to the organic phase. It is more preferable from the viewpoint of haze improvement that it can be used without agglomerating the vanadium dioxide particles.
  • thermochromic film of the present invention comprises vanadium dioxide particles exhibiting thermochromic properties and a block copolymer having a partial structure represented by the following general formula (I).
  • Formula (I) -(A) a-(B) b-(C) c- each represent a repeating unit structure of a monomer constituting the block copolymer.
  • A represents a repeating unit structure of a hydrophobic unsaturated monomer selected from the group consisting of styrenes and alkylene esters.
  • B represents a repeating unit structure of a hydrophilic unsaturated monomer containing a nonionic group.
  • C represents the repeating unit structure of the adsorptive unsaturated monomer containing an amino group or a nitrogen-containing heterocyclic group.
  • a, b and c represent the constituent molar ratio (mol%) of the repeating unit structure of each monomer in the block copolymer, and the total of the constituent molar ratios of a, b and c is 100 mol%. .
  • the repeating unit structure of a monomer means the structure of the bond unit in the polymer when the monomer forms a polymer.
  • A may be a repeating unit structure of a hydrophobic unsaturated monomer selected from the group consisting of styrenes and alkylene esters, such as styrene and styrene derivatives (for example, ⁇ -methylstyrene or vinyltoluene), vinyl ester of carboxylic acid. (E.g. vinyl acetate, vinyl propionate), vinyl halides, ethylenically unsaturated monocarboxylic acids and dicarboxylic acids (e.g.
  • B may be a repeating unit structure of a hydrophilic unsaturated monomer containing a nonionic group, and a monomer having a group selected from the group consisting of a hydroxy group, an alkylene oxide group, and an amide group (for example, hydroxymethyl acrylate, Hydroxyethyl acrylate, acrylamide, methacrylamide, N-methylolacrylamide or methacrylamide, N-alkylacrylamide, and vinylamine amide (eg, vinylformamide, vinylacetamide) are preferable, and are represented by the following general formula (II) It is also preferable to have a structure.
  • a hydrophilic unsaturated monomer containing a nonionic group and a monomer having a group selected from the group consisting of a hydroxy group, an alkylene oxide group, and an amide group (for example, hydroxymethyl acrylate, Hydroxyethyl acrylate, acrylamide, methacrylamide, N-methylolacrylamide or methacryl
  • n represents a number of 1 to 100
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms (eg, methyl, ethyl, n- or iso-isopropyl, n-, iso- or tert-butyl, n-, or neo-pentyl, n- Dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl), or aryl-alkyl group having 1 to 24 carbon atoms (for example, benzyl or phenyl-n-nonyl, alkylaryl having 1 to 24 carbon atoms) , Alkylaryl having 1 to 24 carbon atoms, alkyl having 1 to 24 carbon atoms, and the like.
  • C may be a repeating unit structure of an unsaturated adsorbing monomer containing an amino group or a nitrogen-containing heterocyclic group, and is an unsaturated ethylene containing a primary to quaternary amino group or a nitrogen-containing heterocyclic group.
  • Monomers such as aminoalkyl (meth) acrylate, aminoalkyl (meth) acrylamide (acrylic acid or dimethylaminoethyl methacrylate, acrylic acid or di-t-butylaminoethyl methacrylate, or dimethylaminomethylacrylamide or methacrylamide) , Bitter ionic monomers (eg, sulfopropyl (dimethyl) aminopropyl acrylate, acrylonitrile, 4-aminostyrene, 4-dimethylaminostyrene, 4-vinylpyridine, 2-vinylpyridine and 1-vinylimidazole), It is preferably an ethylenically unsaturated amino monomers selected from the group consisting of methylaminoethyl acrylate, among which, particularly preferably 4-vinyl pyridine.
  • thermochromic film of the present invention contains at least vanadium dioxide particles and a block copolymer having a partial structure represented by the general formula (I), and preferably further contains a hydrophobic binder. .
  • the typical structural example of the thermochromic film of this invention is demonstrated with reference to figures.
  • 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 containing vanadium dioxide particles.
  • a thermochromic film 1 shown in FIG. 1 has a configuration in which an optical functional layer 3 is laminated on a transparent substrate 2.
  • the optical functional layer 3 is present in a state where vanadium dioxide particles are dispersed in the hydrophobic binder B1.
  • 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), dioxide secondary particles VO M of vanadium 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 size by all the particles of the primary particles VO S and secondary particles VO M of vanadium dioxide particles in the optical functional layer 3 is preferably at 200nm or less.
  • the average particle size of the vanadium dioxide particles in the optical functional layer can be determined according to the following method. First, the side surface of the optical functional layer 3 constituting the thermochromic film 1 is trimmed with a microtome to expose a cross section as shown in FIG. Next, the exposed cross section is photographed at 10,000 to 100,000 times using a transmission electron microscope (TEM). The particle size of all vanadium dioxide particles present in a certain area of the photographed cross section is measured. At this time, the vanadium dioxide particles to be measured are preferably in the range of 50 to 100 particles. The shot particles, the primary particles are single particles, as shown in FIG.
  • TEM transmission electron microscope
  • the particle size of the primary particles VO S vanadium dioxide Measure the diameter of each independent particle. If it is not spherical, the projected area of the particle is converted into a circle, and its diameter is taken as the particle size. On the other hand, for vanadium dioxide in which two or more particles are aggregated, the projected area of the entire aggregate is obtained, and then the projected area is converted into a circle, and the diameter is taken as the particle size. The number average diameter is obtained for each diameter of the primary particles and secondary particles obtained as described above.
  • the cut-out cross-sectional portion has a variation in particle distribution, such measurement is performed for 10 different cross-sectional regions, the whole number-average diameter is obtained, and this is the number-average particle size (nm) referred to in the present invention. It was.
  • the particle size of the primary particles is preferably in the range of 10 to 100 nm. Accordingly, the particle size of the secondary particles varies depending on the number of aggregated particles, but is preferably in the range of 50 to 500 nm.
  • the thermochromic film of the present invention preferably has a near-infrared light shielding layer having a function of shielding at least part of the light wavelength range of 700 to 1000 nm in addition to the optical functional layer.
  • Another preferred embodiment of the thermochromic film of the present invention has a hybrid configuration in which the optical functional layer also functions as a resin base material.
  • FIG. 2 is a schematic cross-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 optical functional layer 3 shown in FIG. 1 are formed of the same layer.
  • a primary particle VO S vanadium dioxide is, two or more secondary particles VO M is dispersed in vanadium dioxide particles, in the configuration forming the optical functional layer having both a transparent substrate functions as a single layer .
  • FIG. 3 is a schematic cross-sectional view showing a typical layer arrangement of a thermochromic film having the near-infrared light shielding layer together with the optical functional layer 3 on the transparent substrate in the configuration shown in FIG.
  • the thermochromic film 1 shown in FIG. 3A has a configuration in which the optical functional layer 3, the near-infrared light shielding layer 4, and the transparent substrate 2 are arranged in this order from the light incident side L.
  • the thermochromic film 1 shown in FIG. 3B is an example in which the optical functional layer 3 according to the present invention is disposed between the transparent substrate 2 and the near-infrared light shielding layer 4, and FIG. This is an example in which the near-infrared light shielding layer 4 is disposed on the light incident side L and the optical functional layer 3 according to the present invention is disposed on the back surface side of the transparent substrate 2.
  • thermochromic film of this invention you may provide various functional layers as needed other than each structure layer demonstrated above.
  • the total thickness of the thermochromic film of the present invention is not particularly limited, but is in the range of 10 to 1500 ⁇ m, preferably in the range of 20 to 1000 ⁇ m, more preferably in the range of 30 to 500 ⁇ m, Particularly preferably, it is in the range of 40 to 300 ⁇ m.
  • the visible light transmittance measured by JIS R3106 is preferably 30% or more, more preferably 50% or more, and further preferably 60% or more. It is.
  • thermochromic film of the present invention contains vanadium dioxide particles and a block copolymer having a structure represented by the general formula (I). Furthermore, it is preferable to have a near-infrared light shielding layer having a function of shielding at least part of the light wavelength range of 700 to 1000 nm.
  • 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.
  • optical function layer preferably contains vanadium dioxide particles and a block copolymer having a partial structure represented by the general formula (I).
  • the optical functional layer is preferably present in a state where vanadium dioxide particles are dispersed in a binder resin.
  • the crystal form of the vanadium dioxide particles according to the present invention is not particularly limited, but rutile vanadium dioxide particles (VO 2 particles) may be used from the viewpoint of efficiently expressing thermochromic properties (automatic light control). Is particularly preferred. Since the rutile VO 2 particles have a monoclinic structure below the phase 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 number average particle size of the primary particles and secondary particles of the vanadium dioxide particles in the optical functional layer is preferably 200 nm or less, more preferably in the range of 1 to 180 nm, still more preferably 5 Within the range of ⁇ 100 nm.
  • the average particle diameter of the vanadium dioxide particles can be determined according to the method described above.
  • the primary particle number ratio of vanadium dioxide particles in the optical functional layer which can be determined by the measurement method, is 30% by number or more of the total number of primary particles and secondary particles. Preferably, it is 50% by number or more, particularly preferably 70% by number or more.
  • the ideal upper limit is 100% by number, but the current maximum value is 95% by number or less.
  • the aspect ratio of the vanadium dioxide particles is preferably in the range of 1.0 to 3.0. Since vanadium dioxide particles having such characteristics have a sufficiently small aspect ratio and isotropic shape, the dispersibility when added to a solution is good. In addition, since the single crystal has a sufficiently small particle size, it can exhibit better thermochromic properties than conventional fine particles.
  • vanadium dioxide particles in addition to vanadium dioxide (VO 2 ), for example, 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) and phosphorus (P) It may contain at least one element selected from the group consisting of The addition of such an element is effective in that the phase transition characteristics (particularly the phase transition temperature) of the vanadium dioxide particles can be controlled. 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 concentration of the vanadium dioxide particles in the optical functional layer is not particularly limited, but is generally preferably within the range of 5 to 60% by mass, more preferably 5 to 40% by mass with respect to the total mass of the optical functional layer. %, More preferably in the range of 5 to 30% by mass.
  • the method for producing vanadium dioxide particles includes a method of pulverizing a VO 2 sintered body synthesized by a solid phase method, and a vanadium compound such as divanadium pentoxide (V 2 O 5 ) or ammonium vanadate as a raw material.
  • a vanadium compound such as divanadium pentoxide (V 2 O 5 ) or ammonium vanadate as a raw material.
  • An aqueous synthesis method in which particles are grown while synthesizing VO 2 in a liquid phase using an aqueous solution instead of an organic solvent is preferably used.
  • the aqueous synthesis method is preferable in that the average primary particle size is small and variation in particle size can be suppressed.
  • examples of the aqueous synthesis method include a hydrothermal synthesis method and an aqueous synthesis method using a supercritical state.
  • Details of an aqueous synthesis method using a supercritical state also referred to as a supercritical hydrothermal synthesis method.
  • a supercritical hydrothermal synthesis method also referred to as a supercritical hydrothermal synthesis method.
  • the hydrothermal synthesis method is applied and the aqueous synthesis method is used to prepare an aqueous dispersion containing vanadium dioxide particles, and the vanadium dioxide particles in the aqueous dispersion are dried.
  • the optical functional layer according to the present invention in which the number average particle size of the primary particles and the secondary particles of the vanadium dioxide particles is 200 nm or less by forming the optical functional layer using the coating liquid for forming the optical functional layer in this state. Can be formed.
  • a method for producing vanadium dioxide particles if necessary, fine TiO 2 particles that become the core of particle growth are added as core particles, and vanadium dioxide particles are produced by growing the core particles. You can also.
  • a substance (I) containing vanadium (V), hydrazine (N 2 H 4 ) or a hydrate thereof (N 2 H 4 .nH 2 O), and water are mixed to prepare a solution (A).
  • This solution may be an aqueous solution in which the substance (I) is dissolved in water, or a suspension in which the substance (I) is dispersed in water.
  • the substance (I) examples include divanadium pentoxide (V 2 O 5 ), ammonium vanadate (NH 4 VO 3 ), vanadium trichloride (VOCl 3 ), sodium metavanadate (NaVO 3 ), and the like. .
  • the substance (I) is not particularly limited as long as it is a compound containing pentavalent vanadium (V). Hydrazine (N 2 H 4 ) and its hydrate (N 2 H 4 .nH 2 O) function as a reducing agent for the substance (I) and have a property of being easily dissolved in water.
  • the solution (A) may further contain a substance (II) containing the element to be added.
  • 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).
  • thermochromic properties of the vanadium dioxide particles in particular, the phase transition temperature can be controlled.
  • the solution (A) may further contain a substance (III) having oxidizing property or reducing property.
  • the substance (III) include hydrogen peroxide (H 2 O 2 ).
  • hydrothermal reaction treatment is performed using the prepared solution (A).
  • “hydrothermal reaction” means a chemical reaction that occurs in hot water (subcritical water) whose temperature and pressure are lower than the critical point of water (374 ° C., 22 MPa).
  • the hydrothermal reaction treatment is performed, for example, in an autoclave apparatus.
  • Single crystal fine particles containing vanadium dioxide (VO 2 ) are obtained by the hydrothermal reaction treatment.
  • the conditions of the hydrothermal reaction treatment are set as appropriate, but the temperature of the hydrothermal reaction treatment is, for example, within the range of 250 to 350 ° C. Preferably, it is in the range of 250 to 300 ° C, more preferably in the range of 250 to 280 ° C.
  • the hydrothermal reaction treatment time is preferably in the range of 1 hour to 5 days, for example. Increasing the time can control the particle size and the like of the obtained single crystal fine particles, but an excessively long processing time increases the energy consumption.
  • thermochromic vanadium dioxide VO 2
  • 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 deteriorate during long-term storage, and it is preferable to remove impurities in advance at the stage of the dispersion.
  • the vanadium dioxide particle dispersion As a method for removing impurities in the vanadium dioxide particle dispersion, conventionally known means for separating foreign substances and impurities can be applied.
  • the vanadium dioxide particle dispersion is centrifuged to precipitate vanadium dioxide particles. It is possible to remove impurities in the supernatant and add and disperse the dispersion medium again, or to remove impurities out of the system using an exchange membrane such as an ultrafiltration membrane. From the viewpoint of preventing aggregation, the method using an ultrafiltration membrane is most preferable.
  • Examples of the material for the ultrafiltration membrane include cellulose, polyethersulfone, and polytetrafluoroethylene (abbreviation: PTFE). Among these, polyethersulfone and PTFE are preferably used. By applying and drying the aqueous dispersion from which impurities have been removed, vanadium dioxide particle powder can be obtained.
  • thermochromic film (aqueous)
  • an optical function layer is formed using a wet coating method.
  • the wet coating method include 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, US Pat. No. 2,761791, and the like. Examples thereof include a slide hopper coating method and an extrusion coating method.
  • a solution casting method can be applied, and specific film forming methods include, for example, JP2013-067074A, JP In accordance with the solution casting film forming method described in JP2013-123868A, JP2013-202979A, JP2014-066958A, JP2014-095729A, JP2014-159082A, and the like. Can be formed.
  • thermochromic film (organic solvent system 1)
  • a hydrophobic binder is further added, and coating is performed.
  • -It is also preferable to form an optical functional layer by drying to produce a thermochromic film.
  • the specific production method is the same as the production method of the water-based thermochromic film.
  • thermochromic film (organic solvent system 2)
  • a method for producing a thermochromic film using an organic solvent first, an aqueous dispersion in which vanadium dioxide particles are dispersed without drying an aqueous dispersion in which vanadium dioxide particles are dispersed, obtained by an aqueous synthesis method. An aqueous solution containing a block copolymer is added to the mixture to prepare a mixed solution. Next, an organic solvent is added to the mixed solution to move the vanadium dioxide particles and the block copolymer from the aqueous phase to the organic phase, and the organic phase is separated and extracted.
  • thermochromic film by forming an optical functional layer by mixing a hydrophobic binder with an organic phase and coating and drying is also preferable.
  • a method for transferring the vanadium dioxide particles and the block copolymer from the aqueous phase to the organic phase a general liquid separation operation is performed.
  • thermochromic film of the present invention it is preferable to apply a hydrophobic binder as a binder for holding vanadium dioxide particles.
  • the hydrophobic binder as used in the present invention refers to a resin having a dissolution amount of less than 1.0 g at a liquid temperature of 25 ° C. with respect to 100 g of water, and more preferably a resin having a dissolution amount of less than 0.5 g. More preferably, the resin has a dissolution amount of less than 0.25 g.
  • the hydrophobic binder applied to the present invention is preferably a resin polymerized in a curing treatment step using a hydrophobic polymer or a monomer of a hydrophobic binder.
  • hydrophobic polymer examples include polyethylene, polypropylene, ethylene-propylene copolymer, olefin-based polymer such as poly (4-methyl-1-pentene), acrylate-based copolymer; Halogen-containing polymers such as vinyl and chlorinated vinyl resins; Styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer; polyethylene terephthalate, poly Polyesters such as butylene terephthalate and polyethylene naphthalate; polyamides such as nylon 6, nylon 66 and nylon 610; polyacetal; polycarbonate; polyphenylene oxide; polyphenylene sulfide; Polysulfone; Polysulfone; Polyethersulfone; Polyoxybenzylene; Polyamideimide; ABS resin (acrylonitrile), acrylate
  • hydrophobic binder a resin that is polymerized in a curing process using a monomer of a hydrophobic binder can be exemplified.
  • a typical hydrophobic binder material is a compound that cures upon irradiation with active energy rays. Specific examples include a radical polymerizable compound that is cured by a polymerization reaction with a radical active species and a cationic polymerizable compound that is cured by a cationic polymerization reaction with a cationic active species.
  • radical polymerizable compound examples include a compound having an ethylenically unsaturated bond capable of radical polymerization.
  • examples of the compound having an ethylenically unsaturated bond capable of radical polymerization include acrylic acid, methacrylic acid, itaconic acid, and crotonic acid.
  • Unsaturated carboxylic acids such as isocrotonic acid and maleic acid and their salts, esters, urethanes, amides and anhydrides, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated urethanes, etc. These radically polymerizable compounds are mentioned.
  • cationic polymerizable compound various known cationic polymerizable monomers can be used.
  • cationic polymerizable monomers JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like exemplified in JP-A-2001-220526.
  • photopolymerization initiator it is preferable to contain a photopolymerization initiator together with the above compound.
  • a photopolymerization initiator any known photopolymerization initiators published in “Application and Market of UV / EB Curing Technology” (CMC Publishing Co., Ltd., edited by Yoneho Tabata / edited by Radtech Research Association) may be used. it can.
  • an activity such as ultraviolet rays or electron beams is applied. Irradiate energy rays.
  • ultraviolet LED ultraviolet laser
  • mercury arc lamp xenon arc lamp
  • low pressure mercury lamp fluorescent lamp
  • carbon arc lamp tungsten-halogen copying lamp
  • sunlight can be used.
  • an electron beam it is usually cured with an electron beam having an energy of 300 eV or less, but it can also be cured instantaneously with an irradiation dose of 1 to 5 Mrad.
  • a solvent dispersion containing vanadium dioxide particles in a hydrophobic resin that is a constituent material of the transparent substrate After preparing a dope for film formation by adding and dissolving a solvent, a hybrid optical functional layer that also serves as a resin substrate is prepared by a solution casting method that has been used in the conventional film formation using the dope.
  • a forming method can also be preferably used.
  • thermochromic films examples include resin materials that are conventionally used in the formation of thermochromic films, such as polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polyester such as polyester, polyethylene, polypropylene, cellulose diacetate, cellulose triacetate (abbreviation: TAC), cellulose acetate butyrate, cellulose acetate propionate (abbreviation: CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate, and the like
  • TAC cellulose triacetate
  • CAP cellulose acetate propionate
  • cellulose esters such as cellulose acetate phthalate, cellulose nitrate, and the like
  • polyvinylidene chloride polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate (abbreviation: PC), norbornene tree , Polymethylpentene, polyetherketone, polyimide, polyethersulfone (abbreviation: PES), polyphenylene sulfide, polysulfones, polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon,
  • the solvent is not particularly limited, and examples thereof include methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2- Trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2- Examples include propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, and the like.
  • a hybrid optical functional layer that also serves as a transparent substrate is formed by a solution casting method.
  • additives for optical functional layers Various additives that can be applied to the optical functional layer according to the present invention as long as the effects of the present invention are not impaired are listed below.
  • 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 transparent substrate applicable to the present invention is not particularly limited as long as it is transparent, and examples thereof include glass, quartz, and a transparent resin film. However, it is possible to impart flexibility and suitability for production (manufacturing process suitability). From the viewpoint, a transparent resin film is preferable.
  • “Transparent” in the present invention means that the average light transmittance in the visible light region is 50% or more, preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more.
  • the thickness of the transparent substrate according to the present invention is preferably in the range of 30 to 200 ⁇ m, more preferably in the range of 30 to 100 ⁇ m, and still more preferably in the range of 35 to 70 ⁇ m. If the thickness of the transparent substrate is 30 ⁇ m or more, wrinkles or the like are less likely to occur during handling, and if the thickness is 200 ⁇ m or less, the followability to the curved glass surface when bonded to the glass substrate is improved. .
  • the transparent substrate according to the present invention is preferably a biaxially oriented polyester film, but an unstretched or at least one stretched polyester film can also be used.
  • a stretched film is preferred from the viewpoint of improving strength and suppressing thermal expansion.
  • a stretched film is more preferable.
  • the transparent substrate according to the present invention has a thermal shrinkage within the range of 0.1 to 3.0% at a temperature of 150 ° C. from the viewpoint of preventing generation of wrinkles of the thermochromic film and cracking of the optical functional layer. Preferably, it is in the range of 1.5 to 3.0%, more preferably 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, cycloolefin, polyethylene) , Polypropylene, etc.
  • polyester films for example, polyethylene terephthalate, polyethylene naphthalate, etc.
  • polyvinyl chloride for example, polyethylene terephthalate, polyethylene naphthalate, etc.
  • triacetyl cellulose films, etc. can be used, preferably cycloolefin films, polyester films, triacetyl cellulose films.
  • 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, it is also preferable to provide a near-infrared light shielding layer having a function of shielding at least part of the light wavelength range of 700 to 1000 nm.
  • a near-infrared light shielding layer having a function of shielding at least part of the light wavelength range of 700 to 1000 nm.
  • thermochromic film of this invention can be set as the structure pasted on glass,
  • the glass which bonded this film can be used for a motor vehicle, a rail vehicle, an aircraft, a ship, a building, etc.
  • the glass bonded together can be used for other purposes.
  • the glass on which the film is bonded is preferably used for buildings or vehicles, and can be used for automobile windshields, side glasses, rear glasses, roof glasses, and 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.
  • thermochromic film 101 aqueous
  • aqueous Preparation of vanadium dioxide particle dispersion 1
  • NH 4 VO 3 ammonium vanadate
  • hydrazine hydrate N 2 H 4 ⁇ H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.
  • 5 mass% aqueous solution was slowly added dropwise to prepare a solution X having a pH value of 9.2 at 23 ° C.
  • the prepared solution X is put in a commercially available autoclave for hydrothermal reaction treatment (HU-25 type, manufactured by Sanai Kagaku Co., which has a 25 mL volume Teflon (registered trademark) inner cylinder in a SUS body) at 100 ° C. Hydrothermal reaction treatment was applied for 8 hours, and subsequently at 270 ° C. for 24 hours.
  • HU-25 type manufactured by Sanai Kagaku Co., which has a 25 mL volume Teflon (registered trademark) inner cylinder in a SUS body
  • reaction product was filtered, and the filtration residue was filtered and washed with water and ethanol. Further, this reaction product was dried at 60 ° C. for 10 hours by using a constant temperature dryer to obtain vanadium dioxide particle powder.
  • the obtained vanadium dioxide particle powder and ethanol were subjected to ultrasonic dispersion treatment for 30 minutes with an ultrasonic dispersing machine (UH-300 manufactured by SMT Co., Ltd.) and redispersed, and then a silane coupling agent (KBM- 603: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and a hydrophilic binder resin aqueous solution (PVA105, manufactured by Kuraray Co., Ltd.) are added at a constant temperature of 60 ° C. with a high-speed stirrer.
  • a silane coupling agent KBM- 603: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • PVA105 hydrophilic binder resin aqueous solution
  • vanadium dioxide particle powder having an amine group atomic group.
  • the mass ratio of vanadium dioxide particles / silane coupling agent / hydrophilic binder resin in the obtained vanadium dioxide particle powder was 10: 1: 0.1.
  • coating solution 1 for forming an optical functional layer The following constituent materials were sequentially added, mixed and dissolved to prepare an aqueous optical functional layer forming coating solution 1.
  • 3 mass% vanadium dioxide particle dispersion 1 128 parts by weight 3% by weight boric acid aqueous solution 10 parts by weight 5% by weight hydrophilic binder resin aqueous solution (PVA105, manufactured by Kuraray Co., Ltd.) 60 parts by mass
  • the above-prepared coating solution 1 for forming an optical functional layer has a layer thickness after drying.
  • Wet application was performed under the condition of 1.5 ⁇ m, followed by drying by blowing warm air of 110 ° C. for 2 minutes to form an optical functional layer, and a thermochromic film 101 was produced.
  • thermochromic films 102-105 aqueous
  • vanadium dioxide dispersed in pure water with an ultrasonic disperser UH-300 manufactured by SMT
  • UH-300 ultrasonic disperser
  • Particles were added to the block copolymer solution described in Table 1 so that the vanadium dioxide particle / block copolymer mass ratio was 1: 1, and adjusted to a concentration of 3.0% by mass as vanadium dioxide particles. It was produced in the same manner except that it was changed to (Vanadium dioxide particle dispersions 2 to 5).
  • M-PEGMA represents methoxy-polyethylene glycol (550) monoacrylate.
  • thermochromic film 106 Organic Solvent System 1
  • vanadium dioxide particle dispersion 6 The powder of the vanadium dioxide particles obtained in the preparation of the vanadium dioxide particle dispersion 1 was mixed with the methyl ethyl ketone solution of the block copolymer shown in Table 1 and mixed with an ultrasonic disperser (SMH UH-300) for 30 minutes. The mixture was redispersed by ultrasonic dispersion treatment to prepare a vanadium dioxide particle dispersion 6 having a vanadium dioxide particle / block copolymer mass ratio of 1: 1 and 3% by mass as vanadium dioxide particles.
  • the thermochromic film 106 it produced in the same procedure except having changed the coating liquid 1 for optical function layer formation used by preparation of the thermochromic film 101 into the following coating liquid 2 for optical function layer formation.
  • the prepared solution is put in a commercially available autoclave for hydrothermal reaction treatment (HU-25 type, manufactured by Sanai Kagaku Co., which has a 25 mL volume Teflon (registered trademark) inner cylinder in a SUS body) at 100 ° C. Hydrothermal reaction treatment was performed for 8 hours, and subsequently at 270 ° C. for 24 hours, to prepare an aqueous vanadium dioxide particle aqueous dispersion in which vanadium dioxide particles were dispersed at a concentration of 3.0% by mass.
  • HU-25 type manufactured by Sanai Kagaku Co., which has a 25 mL volume Teflon (registered trademark) inner cylinder in a SUS body
  • the coating liquid 3 for forming an optical functional layer prepared above has a layer thickness after drying. Wet application was performed under the condition of 1.5 ⁇ m, and then dried by blowing hot air at 110 ° C. for 2 minutes to form an optical functional layer, thereby producing a thermochromic film 107 having the configuration shown in FIG. .
  • thermochromic film 108 aqueous
  • the thermochromic film 108 was produced in the same procedure as the thermochromic film 101 except that vanadium dioxide particles containing 0.5% by mass of tungsten were used.
  • thermochromic film 109 aqueous
  • the thermochromic film 109 was produced in the same procedure as the thermochromic film 105 except that vanadium dioxide particles containing 0.5% by mass of tungsten were used.
  • thermochromic film 110 Organic Solvent System 2
  • the thermochromic film 110 was produced in the same procedure as the thermochromic film 107 except that vanadium dioxide particles containing 0.5% by mass of tungsten were used.
  • thermochromic film 111 was produced in the same procedure as the thermochromic film 107 except that vanadium dioxide particles containing 1.0% by mass of molybdenum were used.
  • thermochromic film 112 Organic Solvent System 2
  • the thermochromic film 112 was produced in the same procedure as the thermochromic film 107 except that vanadium dioxide particles containing 1.5% by mass of ruthenium were used.
  • thermochromic film ⁇ Evaluation of thermochromic film> Next, each of the thermochromic films prepared above was subjected to the following evaluations.
  • thermochromic film bonding glass was arrange
  • a thermometer was installed at a position 19 cm away from the thermochromic film-laminated glass inside the heat insulating space, and a 150 W halogen lamp was turned on from a position 10 cm away from the outside where the thermochromic film-laminated glass was placed.
  • the time required for the temperature to rise by 1 ° C. after the halogen lamp was turned on was evaluated according to the following criteria (rank), and the results obtained are shown in Table 1.
  • thermochromic film of the present invention exhibited excellent thermochromic responsiveness with a low haze relative to the comparative example.
  • thermochromic film exhibiting excellent thermochromic response can be produced, and can be suitably used for a near infrared light shielding film and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention vise à proposer un film thermochrome qui présente une grande réactivité thermochrome, mais un voile faible, ainsi qu'un procédé de production dudit film thermochrome. Ce film thermochrome est caractérisé en ce qu'il contient des particules de dioxyde de vanadium thermochrome et un copolymère séquencé présentant une structure partielle représentée par la formule générale (I). Formule générale (I) : -(A)a-(B)b-(C)c-
PCT/JP2016/076629 2015-10-27 2016-09-09 Film thermochrome et procédé de production d'un film thermochrome WO2017073183A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114539469A (zh) * 2022-02-24 2022-05-27 重庆禾维科技有限公司 一种可逆热致变色粉末的合成方法及具有其的调光板/薄膜和应用

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CN112624628A (zh) * 2020-12-17 2021-04-09 陈治兰 一种温致变色夹层玻璃及其制备方法

Citations (4)

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JP2002145612A (ja) * 2000-11-01 2002-05-22 Ube Ind Ltd 薄膜とその製造方法
JP2011136873A (ja) * 2009-12-28 2011-07-14 Tsurumi Soda Co Ltd 二酸化バナジウム微粒子、その製造方法、及びサーモクロミックフィルム
JP2012141353A (ja) * 2010-12-28 2012-07-26 Hiraoka & Co Ltd 可変遮熱性採光シート
JP2014062236A (ja) * 2012-08-29 2014-04-10 Tokyo Univ Of Science 構造色発色基材及びその作製方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002145612A (ja) * 2000-11-01 2002-05-22 Ube Ind Ltd 薄膜とその製造方法
JP2011136873A (ja) * 2009-12-28 2011-07-14 Tsurumi Soda Co Ltd 二酸化バナジウム微粒子、その製造方法、及びサーモクロミックフィルム
JP2012141353A (ja) * 2010-12-28 2012-07-26 Hiraoka & Co Ltd 可変遮熱性採光シート
JP2014062236A (ja) * 2012-08-29 2014-04-10 Tokyo Univ Of Science 構造色発色基材及びその作製方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114539469A (zh) * 2022-02-24 2022-05-27 重庆禾维科技有限公司 一种可逆热致变色粉末的合成方法及具有其的调光板/薄膜和应用

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