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WO2018163809A1 - Film thermochromique et corps composite à film thermochromique - Google Patents

Film thermochromique et corps composite à film thermochromique Download PDF

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Publication number
WO2018163809A1
WO2018163809A1 PCT/JP2018/006106 JP2018006106W WO2018163809A1 WO 2018163809 A1 WO2018163809 A1 WO 2018163809A1 JP 2018006106 W JP2018006106 W JP 2018006106W WO 2018163809 A1 WO2018163809 A1 WO 2018163809A1
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Prior art keywords
thermochromic film
thermochromic
vanadium dioxide
compound
film
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Ceased
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PCT/JP2018/006106
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English (en)
Japanese (ja)
Inventor
▲高▼　友香子
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to JP2019504442A priority Critical patent/JPWO2018163809A1/ja
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/0147—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on thermo-optic effects
    • 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
    • B32B17/10—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 of synthetic resin
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/20—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising esters
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2419/00—Buildings or parts thereof
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings

Definitions

  • the present invention relates to a thermochromic film and a thermochromic film composite, and more particularly to a thermochromic film that suppresses the increase in haze and has excellent weather resistance, and a thermochromic film composite including the same.
  • Near-infrared light shielding film is an effective means for energy saving because it can reduce the load on cooling equipment such as air conditioners in the car by applying it to the window glass of car bodies and buildings.
  • the near-infrared light shielding film is preferably used due to its high near-infrared light shielding effect in the low-latitude zone near the equator where the illuminance of sunlight is high.
  • incident light may be uniformly shielded even when it is desired to capture sunlight as much as possible in the vehicle or indoors.
  • thermochromic material in which the optical properties of near-infrared light shielding and transmission are controlled by temperature has been studied.
  • a typical example of the material is vanadium dioxide (hereinafter also referred to as “VO 2 ”) used in Patent Documents 1 and 2. Vanadium dioxide is known to undergo a phase transition in the temperature range of about 50 to 60 ° C. and exhibit thermochromic properties.
  • Patent Document 3 uses vanadium dioxide-containing particles dispersed in a glycerin ester by adjusting the phase transition temperature by doping vanadium dioxide-containing particles with at least one atom selected from tungsten, molybdenum, niobium and tantalum.
  • An interlayer film for laminated glass has also been proposed.
  • vanadium dioxide promotes oxidation of vanadium dioxide and change in crystal structure by moisture and oxygen in the atmosphere.
  • thermochromic films containing vanadium dioxide-containing particles There is a problem of deterioration in weather resistance such as an increase in color and a change in color tone when stored for a long period of time in a high temperature and high humidity environment.
  • Patent Document 4 it is reported that by using vanadium dioxide-containing particles containing a metal alkoxide, the haze is low and the weather resistance such as crack resistance, adhesion and thermochromic stability after long-term storage is improved. However, there is still room for improvement in the suppression of the haze and weather resistance deterioration.
  • JP 2004-346260 A Japanese Patent No. 6004418 Japanese Patent Application Laid-Open No. 2012-0.25630 JP 2016-188939 A
  • the present invention has been made in view of the above-described problems and circumstances, and a solution to the problem is to provide a thermochromic film that suppresses an increase in haze and has excellent weather resistance, and a thermochromic film composite including the thermochromic film. That is.
  • thermochromic film having an optical functional layer containing vanadium dioxide-containing particles exhibiting thermochromic properties on at least a base material in the process of examining the cause of the above problems and the like in order to solve the above problems.
  • thermochromic film containing the specific compound in the optical functional layer was found to suppress the increase in haze and obtain a thermochromic film excellent in weather resistance.
  • thermochromic film having an optical functional layer containing at least vanadium dioxide-containing particles exhibiting thermochromic properties on a substrate, wherein the optical functional layer further contains an acrylic resin and a polymer dispersant.
  • a thermochromic film having an optical functional layer containing at least vanadium dioxide-containing particles exhibiting thermochromic properties on a substrate, wherein the optical functional layer further contains an acrylic resin and a polymer dispersant.
  • thermochromic film according to item 1 wherein the vanadium dioxide-containing particles have a number average particle diameter in the range of 30 to 200 nm.
  • thermochromic film according to Item 1 or 2 wherein the optical functional layer further contains an aluminum chelating agent.
  • thermochromic film according to any one of Items 1 to 3, wherein the polymer dispersant is a polymer polyamine-based dispersant.
  • thermochromic film according to any one of Items 1 to 4, wherein the optical functional layer further contains a titanium chelating agent.
  • thermofunctional film according to any one of items 1 to 5, wherein the optical functional layer further contains a polyfunctional thiol compound.
  • thermochromic film according to item 3 wherein the aluminum chelating agent is a compound having a partial structure represented by the following chemical formula (A).
  • thermochromic film according to any one of Items 1 to 7, wherein the acrylic resin is a polyfunctional acrylate compound.
  • thermochromic film according to item 8 wherein the polyfunctional acrylate compound is a polyfunctional pentaerythritol (meth) acrylate compound.
  • thermochromic composite comprising the thermochromic film according to any one of items 1 to 9.
  • thermochromic film that suppresses the increase in haze and has excellent weather resistance
  • thermochromic film composite including the thermochromic film
  • the acrylic resin used as the binder resin has a high affinity with the vanadium dioxide-containing particles, and can be expected to prevent the particles from agglomerating even when the film is dried.
  • the use of the polymer dispersant improves the dispersibility of the vanadium dioxide-containing particles in the binder resin, and the vanadium dioxide-containing particles have a low affinity for organic solvents. It is presumed that dispersibility is improved by adding.
  • the use of a polyamine-based dispersant as the polymer dispersant has a high effect of suppressing aggregation of vanadium dioxide-containing particles due to the charge because the surface of the vanadium dioxide-containing particles is negatively charged. It is considered a thing.
  • vanadium dioxide-containing particles having a number average particle diameter in the range of 30 to 200 nm which is excellent in thermochromic properties
  • the use of a polyamine-based dispersant suppresses aggregation between the particles and reduces haze. It is assumed that the increase can be suppressed.
  • weather resistance is also improved by further containing an aluminum chelating agent.
  • the mechanism is considered as follows.
  • An optical functional layer made of acrylic resin as a binder resin has low water absorption as a film, and the polymer dispersant and aluminum chelating agent are easily adsorbed to the vanadium dioxide-containing particles, so that oxidation of vanadium dioxide by moisture is suppressed and weather resistance. Is estimated to have improved. Furthermore, it is guessed that a weather resistance improves more by the same effect by containing a titanium chelating agent and a polyfunctional thiol compound.
  • thermochromic film of the present invention Schematic which shows an example of the flow-type reaction apparatus which comprises the hydrothermal reaction part applicable to manufacture of the vanadium dioxide containing particle
  • the schematic sectional drawing which shows an example of a structure of the thermochromic composite body which comprised the thermochromic film of this invention
  • thermochromic film of the present invention is a thermochromic film having an optical functional layer containing vanadium dioxide-containing particles exhibiting at least thermochromic properties on a base material, the optical functional layer further comprising an acrylic resin and a polymer dispersion And an agent.
  • This feature is a technical feature common to or corresponding to the claimed invention.
  • the number average particle diameter of the vanadium dioxide-containing particles is in the range of 30 to 200 nm to reduce haze as a thermochromic film. ,preferable.
  • the optical functional layer further contains an aluminum chelating agent because the aluminum chelating agent is adsorbed on the vanadium dioxide-containing particles and the weather resistance can be improved by suppressing oxidation of vanadium dioxide by moisture. It is an aspect.
  • the polymer dispersant is preferably a polymer polyamine-based dispersant, which can remarkably suppress aggregation of vanadium dioxide-containing particles in terms of charge, and is preferable from the viewpoint of further suppressing haze increase. This is an embodiment.
  • the optical functional layer further contains a titanium chelating agent, and further contains a polyfunctional thiol compound, it is easily adsorbed to the vanadium dioxide-containing particles, and thus has the same effect as the aluminum chelating agent.
  • the weather resistance can be further improved, which is a preferred embodiment.
  • the aluminum chelating agent is a compound having a partial structure represented by the chemical formula (A), because the ability to adsorb by the vanadium dioxide-containing particles is high, and the effect of improving the weather resistance is exhibited.
  • the acrylic resin is a polyfunctional acrylate compound, and among them, the use of a polyfunctional pentaerythritol (meth) acrylate compound has a high affinity with vanadium dioxide-containing particles as a binder resin, and even when drying a film. From the viewpoint of the effect of preventing aggregation, it is a preferred embodiment.
  • thermochromic composite of the present invention is characterized by comprising the thermochromic film 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 having an optical functional layer containing vanadium dioxide-containing particles exhibiting at least thermochromic properties on a base material, the optical functional layer further comprising an acrylic resin and a polymer dispersion And an agent.
  • thermochromic film of the present invention will be described with reference to the drawings.
  • thermochromic film of the present invention is a configuration in which an optical functional layer is formed on a transparent substrate.
  • FIG. 1 is a schematic sectional view showing an example of the configuration of the thermochromic film of the present invention.
  • thermochromic film 1 of the present invention has a configuration in which an optical functional layer 3 is laminated on a transparent substrate 2.
  • the optical functional layer 3 is in a state in which vanadium dioxide-containing particles are dispersed in the acrylic resin B that functions as a binder resin.
  • the form of the vanadium dioxide-containing particles, the primary particles vanadium dioxide-containing particles are present independently (displayed in Figure 1 and VO S), a collection of two or more of vanadium dioxide-containing particles (aggregates also referred.) there is a configured secondary particles (displayed in Figure 1 and VO M) as.
  • Secondary particles (VO M ) are also referred to as secondary particle aggregates or secondary aggregate particles.
  • the optical functional layer 3 according to the present invention is characterized in that the dispersion of the primary particles and the secondary particles of the vanadium dioxide-containing particles in the acrylic resin further contains a polymer dispersant.
  • FIG. 1 is an example of the minimum configuration of the thermochromic film of the present invention, and may have an undercoat layer, an intermediate layer or the like between the substrate 2 and the optical functional layer 3, and the optical functional layer 3 A hard coat layer, an antireflection layer, an antistatic layer, or the like may be provided thereon. Furthermore, you may have the backcoat layer for improving slipperiness
  • FIG. 1 is an example of the minimum configuration of the thermochromic film of the present invention, and may have an undercoat layer, an intermediate layer or the like between the substrate 2 and the optical functional layer 3, and the optical functional layer 3 A hard coat layer, an antireflection layer, an antistatic layer, or the like may be provided thereon. Furthermore, you may have the backcoat layer for improving slipperiness
  • the visible light transmittance measured by JIS R 3106: 1998 is preferably 20% or more, more preferably 40% or more.
  • the visible light transmittance often varies depending on the application.
  • thermochromic film of the present invention will be described.
  • optical functional layer is characterized by containing an acrylic resin and a polymer dispersant functioning as a binder resin together with at least vanadium dioxide-containing particles exhibiting thermochromic properties.
  • Vanadium dioxide-containing particles Vanadium oxide constituting vanadium dioxide-containing particles is an embodiment of vanadium oxide.
  • Vanadium oxide takes various forms in nature, for example, 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 Examples of the structure include 3+ , V 2 O 3 , V 2+ , VO, and V.
  • the form changes depending on the environmental atmosphere. Generally, V 2 O 5 is formed in an oxidizing environment, and 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.
  • rutile vanadium dioxide-containing particles (hereinafter also simply referred to as VO 2 -containing particles) from the viewpoint of efficiently expressing thermochromic properties.
  • the rutile vanadium dioxide-containing particles have a monoclinic structure below the transition temperature, they are also called M-type.
  • the vanadium dioxide-containing particles according to the present invention are dispersed in the optical functional layer so that the number average particle diameters of the primary particles (VO S ) and secondary particles (VO M ) are in the range of 30 to 200 nm. It is preferable from the viewpoint of the effect of reducing haze.
  • the particle diameter measurement method various measurement methods can be applied, but in the present invention, measurement is preferably performed according to a dynamic light scattering method.
  • the number average particle size (nm) can be measured by a dynamic light scattering (Dynamic Light Scattering, DLS) method using a commercially available dynamic light scattering analyzer.
  • DLS Dynamic Light Scattering
  • a dispersion containing vanadium dioxide-containing particles and water is mixed with water so that the concentration of the vanadium dioxide-containing particles is 0.01% by mass with respect to the total mass of the dispersion to prepare a sample for particle size measurement. .
  • the hydrodynamic diameter (nm) of the prepared particle size measurement sample was measured by a dynamic light scattering (DLS) method using a dynamic light scattering analyzer (DLS-8000, manufactured by Otsuka Electronics Co., Ltd.). Based on this measurement, the number average particle size of the particle size distribution by cumulant analysis is obtained.
  • DLS dynamic light scattering
  • the preferred number average particle diameter of the primary particles and secondary particles in the vanadium dioxide-containing particles according to the present invention is preferably in the range of 30 to 200 nm. Those having an average particle size of less than 30 nm are difficult to synthesize and control of the particle size tends to be complicated. On the other hand, when an average particle diameter exceeds 200 nm, the initial haze of the obtained thermochromic film will rise and transparency (total light transmittance) will become inadequate.
  • the average particle diameter is preferably 30 to 100 nm, more preferably 30 to 50 nm.
  • vanadium dioxide-containing particles having such characteristics have a small single crystal particle size, they can exhibit better thermochromic properties than conventional particles.
  • the vanadium dioxide-containing particles according to the present invention are preferably vanadium dioxide-containing particles having a chemical composition represented by the following formula (Vo).
  • M represents tungsten (W), molybdenum (Mo), magnesium (Mg), iron (Fe), nickel (Ni), aluminum (Al), fluorine (F), and phosphorus (P).
  • An element selected from the group consisting of x represents a numerical value satisfying 0 ⁇ x ⁇ 0.1.
  • the total amount of the above elements with respect to the finally obtained vanadium dioxide-containing particles is preferably about 0.1 to 10.0 atomic% with respect to vanadium (V) atoms.
  • a vanadium (IV) -containing compound is used as the vanadium-containing compound, and an alkali is used as the compound that reacts with the vanadium-containing compound. This is preferable in that vanadium dioxide-containing particles can be formed.
  • the method of using a vanadium (V) -containing compound as the vanadium-containing compound and applying a reducing agent as the compound that reacts with the vanadium-containing compound similarly forms stable and highly monodispersed vanadium dioxide-containing particles. It is preferable at the point which can do.
  • the vanadium dioxide-containing particles are separated from each other without drying the vanadium dioxide-containing particles in the dispersion after preparing the dispersion containing the vanadium dioxide-containing particles. It is preferable to prepare a coating solution for forming an optical functional layer by mixing with a binder resin solution in a dispersed state.
  • the method for producing vanadium dioxide-containing particles is not particularly limited, but as an example, using a flow reactor having a hydrothermal reaction section, a vanadium-containing compound and deaerated water (or ion exchange) Water), a reaction solution obtained by mixing a compound that reacts with the vanadium-containing compound dissolved in deaerated water, and deaerated water (or ion-exchanged water) in a supercritical or subcritical state, A method of producing vanadium dioxide-containing particles by a thermal synthesis method is preferred.
  • a method in which a vanadium-containing compound is hydrothermally reacted in the presence of supercritical or subcritical degassed water (or ion-exchanged water) to form vanadium dioxide-containing particles is referred to as “hydrothermal synthesis method”.
  • “ Hydrothermal reaction method ” and“ hydrothermal reaction ”
  • the implementation steps are also referred to as“ hydrothermal reaction steps ”.
  • the method for producing vanadium dioxide-containing particles comprises a hydrothermal reaction using degassed water (or ion-exchanged water) and a flow-type reaction having a hydrothermal reaction section.
  • a method performed using an apparatus is preferred.
  • degassed water is used as dissolved water
  • a flow reactor a preferred mode for performing a hydrothermal reaction using a flow reactor.
  • the present invention is not limited to the following form.
  • thermochromic and monodispersed vanadium dioxide-containing particles by carrying out in the presence of degassed water in a supercritical or subcritical state at high pressure in the hydrothermal reaction section And the transparency of the thermochromic film can be achieved.
  • the reason for this is that the hydrothermal reaction is carried out in the presence of degassed water in a supercritical or subcritical state under high pressure, thereby suppressing the oxidizing atmosphere during the hydrothermal reaction and reducing the vanadium dioxide having the desired valence.
  • Vanadium dioxide (VO 2 ) -containing particles that can be produced by a stable reaction and have thermochromic properties can be produced stably.
  • a hydrothermal reaction When a hydrothermal reaction is performed using a flow reactor, in the hydrothermal reaction section that performs the hydrothermal reaction of the flow reactor, a raw material liquid containing a vanadium-containing compound and deaerated water, and the reaction with the vanadium-containing compound are reacted.
  • the passage time of the reaction solution in which the compound to be mixed and degassed water in a supercritical or subcritical state is mixed is preferably in the range of 4 to 700 seconds, and more preferably in the range of 12 to 700 seconds.
  • the reaction liquid basically includes (1) a raw material liquid containing a vanadium-containing compound (A) and deaerated water, (2) a compound (B) that reacts with the vanadium-containing compound, and (3 ) Supercritical or subcritical degassed water, but at least (1) a raw material liquid containing vanadium-containing compound (A) and degassed water, and (3) supercritical or subcritical degassed
  • a preferred embodiment is a mode in which water is divided into constituent requirements and (1) or (3) is combined with (2) a compound (B) that reacts with a vanadium-containing compound.
  • the raw material liquid container contains (1) a raw material liquid containing a vanadium-containing compound (A) and degassed water, and (2) a compound (B) that reacts with the vanadium-containing compound, for example, degassed
  • A vanadium-containing compound
  • B a compound that reacts with the vanadium-containing compound
  • An alkali or reducing agent dissolved in water at a predetermined concentration is added, deaerated water is added as water to the other raw material liquid container, and this deaerated water is supercritical under a predetermined temperature and pressure with a heating medium.
  • a raw material liquid containing (1) a vanadium-containing compound (A) and degassed water is added to the raw material liquid container, and (2) a compound that reacts with the vanadium-containing compound in the other raw material liquid container
  • the deaerated water containing (B) is added, and the deaerated water containing the compound (B) that reacts with the vanadium-containing compound is removed from the supercritical or subcritical state with a heating medium at a predetermined temperature and pressure.
  • FIG. 2 is a schematic view showing an example of a flow-type reaction apparatus having a hydrothermal reaction section that can be applied to the production of vanadium dioxide-containing particles according to the present invention.
  • a flow reactor (101) having a hydrothermal reaction section is composed of a raw material liquid containing vanadium-containing compound (A) and a compound (B) that reacts with the vanadium-containing compound and degassed water.
  • Embodiment 1 or a raw material liquid container 1 (105) for containing a raw material liquid (Embodiment 2) containing a vanadium-containing compound (A) and deaerated water, supercritical water or subcritical water as the other constituent liquid Degassed water for forming (Embodiment 1) or raw material liquid container 2 (102) for containing degassed water (Embodiment 2) containing a compound (B) that reacts with a vanadium-containing compound, hydrothermal reaction Hydrothermal reaction section (116) having heating medium (114) to be performed, tank (109) for containing reaction liquid after hydrothermal reaction, raw material liquid container 1 (105), raw material liquid container 2 (102) and tank ( 109) Channel (pipe, 103 and 106), one of the raw material liquid liquid container
  • the deaerated water or the like for forming the supercritical water or subcritical water is supplied from the raw material liquid container 2 (102) to the pipe (103), the heating medium (113), the confluence (MP), the heating part pipe ( 117), a pipe (118), and a pump (104) for feeding liquid to the tank (109) via the control valve (119).
  • the flow reaction device (101) includes a cooling unit (108) including a flow path (118) for cooling the reaction liquid containing the vanadium dioxide-containing particles after the hydrothermal reaction, if necessary. Also good. Moreover, although mentioned later for details, it mixes with the reaction liquid after the surface modifier, pH adjuster, or hydrothermal reaction added to the reaction liquid containing the vanadium dioxide containing particle
  • a tank (110) for containing a cooling medium (for example, water) for cooling, a surface modifier, a pH adjusting agent, a cooling medium, etc. is sent to the flow path (118) via the flow path (111).
  • a pump (112) may be further included.
  • the flow reactor (101) has heating media (113, 115) in the line of the flow path (106) or the flow path (103).
  • the heating medium (113) arranged in the flow path (103) applies superheated water or degassed water stored in the raw material liquid container 2 (102) to a predetermined temperature and pressure. Form subcritical water.
  • hydrothermal reaction step in the hydrothermal reaction step, 1) A reaction liquid obtained by mixing a vanadium-containing compound (A), a raw material liquid containing a compound (B) that reacts with a vanadium-containing compound and degassed water, and degassed water in a supercritical or subcritical state, or 2) A reaction liquid obtained by mixing a raw material liquid containing a vanadium-containing compound (A) and deaerated water and a supercritical or subcritical deaerated water containing a compound (B) that reacts with the vanadium-containing compound.
  • vanadium dioxide-containing particles are obtained by hydrothermal reaction in the presence of supercritical water or subcritical water.
  • the compound (B) that reacts with the vanadium-containing compound (A) is not particularly limited as long as it can produce vanadium dioxide-containing particles by hydrothermal reaction of the raw material liquid. Agents and the like.
  • a tetravalent vanadium (IV) -containing compound is used as the vanadium-containing compound (A)
  • an alkali is applied as the compound (B) that reacts with the vanadium-containing compound (A).
  • the alkali is added to the raw material liquid containing the vanadium-containing compound (A) and water.
  • the alkali is added to water for forming supercritical or subcritical water.
  • the compound (B) that reacts with the vanadium-containing compound (A) includes a reducing agent (for example, hydrazine and its It is preferable to apply a hydrate or the like.
  • the reducing agent is added to the raw material liquid containing the vanadium-containing compound (A) and water in the first embodiment, and added to water for forming supercritical or subcritical water.
  • the water applied to the hydrothermal reaction is deaerated water. More specifically, the water constituting the reaction solution containing the vanadium-containing compound (A) that passes through the hydrothermal reaction section and the compound (B) that reacts with the vanadium-containing compound (A) is deaerated water.
  • the deaerated water here is water having an amount of dissolved oxygen at 25 ° C.
  • the reaction solution in the method for producing vanadium dioxide-containing particles, in the hydrothermal reaction step, is hydrothermally reacted to form vanadium dioxide-containing particles.
  • hydrothermal reaction as used herein means a mineral synthesis or alteration reaction, that is, a chemical reaction performed in the presence of high-temperature water, particularly high-temperature and high-pressure water.
  • the hydrothermal reaction in the present invention is performed in a state where the temperature is 150 ° C. or higher and the pressure is higher than the saturated vapor pressure, that is, the deaerated water exists in a supercritical or subcritical state. Is preferred. It is known that by performing the reaction under such high-temperature and high-pressure conditions, a unique reaction occurs due to the presence of degassed water, unlike the case of normal pressure and high temperature where almost no degassed water can exist. Yes. It is also known that the solubility of oxides such as silica and alumina is improved and the reaction rate is improved.
  • the number average particle diameter and particle size distribution of the vanadium dioxide-containing particles formed can be narrowed, and the vanadium dioxide-containing particles
  • the transparency of the optical film containing thermochromic properties and vanadium dioxide-containing particles can be improved (decrease in haze).
  • Acrylic resin The present invention is characterized in that the optical functional layer contains an acrylic resin, and preferably contains a polyfunctional acrylate compound. Furthermore, the polyfunctional acrylate compound preferably contains a polyfunctional pentaerythritol (meth) acrylate compound.
  • the acrylic resin according to the present invention is a compound containing an acrylic resin or an acrylic monomer component.
  • the acrylic resin according to the present invention is a polymer of acrylic acid ester or methacrylic acid ester, and includes a copolymer with other monomers.
  • the acrylic resin according to the present invention includes a methacrylic resin.
  • the resin is not particularly limited, but the methyl methacrylate unit is in the range of 50 to 99% by mass, and other monomer units copolymerizable therewith are in the range of 1 to 50% by mass. Is preferred.
  • alkyl methacrylates having 2 to 18 alkyl carbon atoms alkyl acrylates having 1 to 18 carbon atoms, isobornyl methacrylate, 2-hydroxy Hydroxyalkyl acrylates such as ethyl acrylate, ⁇ , ⁇ -unsaturated acids such as acrylic acid and methacrylic acid, acrylamides such as acryloylmorpholine, Nhydroxyphenyl methacrylamide, N-vinylpyrrolidone, maleic acid, fumaric acid, itaconic acid, etc.
  • Unsaturated divalent carboxylic acid aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile, maleic anhydride, maleimide, N-substituted maleimide, glutarimide , Glutaric anhydride, etc. Is mentioned.
  • Examples of the copolymerizable monomer that forms a unit excluding glutarimide and glutaric anhydride from the above units include monomers corresponding to the above units. That is, alkyl methacrylate having 2 to 18 carbon atoms, alkyl acrylate having 1 to 18 carbon atoms, hydroxyalkyl acrylate such as isobornyl methacrylate and 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, etc.
  • ⁇ , ⁇ -Unsaturated acids acrylamides such as acryloylmorpholine, N-hydroxyphenylmethacrylamide, divalent carboxylic acids containing unsaturated groups such as N-vinylpyrrolidone, maleic acid, fumaric acid, itaconic acid, styrene, ⁇ -methylstyrene And monomers such as ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile, maleic anhydride, maleimide, and N-substituted maleimide.
  • acrylamides such as acryloylmorpholine, N-hydroxyphenylmethacrylamide
  • divalent carboxylic acids containing unsaturated groups such as N-vinylpyrrolidone
  • maleic acid fumaric acid, itaconic acid
  • styrene ⁇ -methylstyrene
  • monomers such as ⁇ , ⁇ -unsaturated nit
  • the glutarimide unit can be formed, for example, by reacting a primary amine (imidizing agent) with an intermediate polymer having a (meth) acrylic acid ester unit (see JP 2011-26563 A). ).
  • the glutaric anhydride unit can be formed, for example, by heating an intermediate polymer having a (meth) acrylic ester unit (see Japanese Patent No. 496164).
  • acrylic resin according to the present invention among the above structural units, from the viewpoint of mechanical strength, isobornyl methacrylate, acryloylmorpholine, N-hydroxyphenylmethacrylamide, N-vinylpyrrolidone, styrene, hydroxyethyl methacrylate, maleic anhydride It is particularly preferred that an acid, maleimide, N-substituted maleimide, glutaric anhydride or glutarimide is included.
  • the acrylic resin according to the present invention is an improvement in the viewpoint of controlling the dimensional change with respect to the change in environmental temperature and humidity atmosphere, the peelability from the metal support during film production, the drying property of the organic solvent, the heat resistance and the mechanical strength.
  • the weight average molecular weight (Mw) is preferably in the range of 50,000 to 1,000,000, more preferably in the range of 100,000 to 1,000,000, and in the range of 200,000 to 800,000. It is particularly preferred.
  • the heat resistance and mechanical strength are excellent, and if it is 1,000,000 or less, the drying property of the solvent is excellent.
  • the weight average molecular weight (Mw) of the acrylic resin according to the present invention can be measured by gel permeation chromatography.
  • the measurement conditions are as follows.
  • the method for producing the acrylic resin according to the present invention is not particularly limited, and any known method such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization may be used.
  • a polymerization initiator a normal peroxide type and an azo type can be used, and a redox type can also be used.
  • suspension or emulsion polymerization may be carried out within a range of 30 to 100 ° C.
  • bulk or solution polymerization may be carried out within a range of 80 to 160 ° C.
  • polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent.
  • the glass transition temperature Tg of the acrylic resin is preferably in the range of 80 to 120 ° C. from the viewpoint of maintaining the mechanical strength of the film.
  • acrylic resins can be used as the acrylic resin according to the present invention.
  • Delpet 60N, 80N, 980N, SR8200 above, manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Dianal BR52, BR80, BR83, BR85, BR88, EMB-143, EMB-159, EMB-160, EMB-161, EMB-218, EMB-229, EMB-270, EMB-273 Mitsubishi Rayon Co., Ltd.
  • KT75, TX400S IPX012 (Electric Chemical Industry Co., Ltd.)
  • BL-616, WXU-880 Above, manufactured by DIC Corporation.
  • Two or more acrylic resins can be used in combination.
  • the acrylic resin according to the present invention preferably contains a polyfunctional acrylate compound, among others.
  • a polyfunctional acrylate compound An acrylic compound in which a hydroxy group of a polyhydric alcohol compound is substituted with a (meth) acryloyl group is known as a polyfunctional acrylate, and since the polymer formed due to polyfunctionality forms a three-dimensional structure, a strong structure is obtained.
  • the acrylic resin having a polar group is preferably a resin containing a repeating unit derived from a compound containing a polar group and a (meth) acryloyl group.
  • a polar group indicates that the difference in electronegativity of two atoms bonded to each other is large. Specifically, a hydroxy group, C ⁇ O, —COOH, —NH 2 , —NO 2 , —NH 3 + , -CN and the like are mentioned, and a hydroxy group is preferable.
  • the acrylic resin having a polar group in the present invention may contain a repeating unit having no polar group, or may contain a repeating unit other than a repeating unit derived from a compound containing a (meth) acryloyl group. Good.
  • acrylic compound in which at least one hydroxy group of the polyhydric alcohol compound is substituted with a (meth) acryloyl group three or more (meth) per molecule are used from the viewpoint of improving adhesion to a support and film strength.
  • a polyfunctional acrylic resin having an acryloyl group is preferred.
  • a compound having three or more functional groups in one molecule a compound having a polymerizable functional group (polymerizable unsaturated double bond) such as a (meth) acryloyl group, a vinyl group, a styryl group, or an allyl group.
  • a compound having a (meth) acryloyl group and —C (O) OCH ⁇ CH 2 is preferable.
  • Particularly preferred are polyfunctional acrylate compounds containing three or more (meth) acryloyl groups in one molecule described below.
  • polyfunctional acrylate compounds particularly preferred polyfunctional pentaerythritol (meth) acrylate compounds are particularly limited as long as they have a pentaerythritol skeleton and the (meth) acrylate component has two or more functional groups. Is not to be done.
  • (meth) acrylate means methacrylate or acrylate.
  • Examples of the polyfunctional pentaerythritol (meth) acrylate compound according to the present invention include pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth).
  • Examples include acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, and dipentaerythritol di (meth) acrylate.
  • a monomer obtained by further modifying propionic acid, propylene oxide, ethylene oxide, caprolactone or the like can be used.
  • These polyfunctional pentaerythritol (meth) acrylate compounds may be used alone or in admixture of two or more.
  • polyfunctional acrylate compounds having a (meth) acryloyl group include KAYARAD® PET30, KAYARAD® DPHA, DPCA-30, DPCA-120 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-305 manufactured by Toagosei Co., Ltd. , M313, M450, and the like.
  • urethane acrylate include U15HA, U4HA and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EB5129 manufactured by Daicel UCB Corporation.
  • the hydroxy group value of the acrylic resin is preferably 5.0 to 40.0 mgKOH / g. When it is 5.0 mgKOH / g or more, the affinity with the vanadium dioxide particles is excellent, and when it is 40.0 mgKOH / g or less, the weather resistance of the vanadium dioxide particles is improved.
  • the acid value is preferably 1.0 to 6.0 mgKOH / g. Within such a range, the weather resistance becomes good, which is preferable.
  • Specific methods for measuring the hydroxy group value and the acid value include, for example, the method described in JIS 0070-1992.
  • the use amount of the acrylic resin according to the present invention is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass when the total solid content of the composition for forming an optical functional layer is 100 parts by mass. is there. If the amount of the polyfunctional pentaerythritol (meth) acrylate is 10 parts by mass or more, a desired film hardness can be obtained. Moreover, if it is 90 mass parts or less, a flexible film
  • the optical functional layer according to the present invention is characterized in that a polymer dispersant is contained for the purpose of improving the dispersibility of the vanadium dioxide-containing particles.
  • polymer dispersant examples include those in the oligomer region having a molecular weight of about 2000 or more.
  • polycarboxylic acid-based, polyether-based, polyamine-based, and the like can be mentioned.
  • the dispersant for vanadium dioxide-containing particles polyamine-based is preferable.
  • the polymer polyamine compound examples include polyalkylene polyamine and polyoxyethylene alkylamine.
  • the molecular weight is preferably 500 or more and less than 10,000 from the viewpoint of dispersibility.
  • the content of the polymer polyamine compound is preferably 8 to 120% by mass, more preferably 10 to 100% by mass, based on the content of the vanadium dioxide-containing particles. If it is 8% by mass or more, an effect of improving haze can be expected, and if it is 120% by mass or less, a change in color tone can also be suppressed.
  • the polyamine dispersant used in the present invention preferably has an acid value of 10 to 30 mgKOH / g and an amine value of 5 to 50 mgKOH / g.
  • the acid value of the polyamine dispersant is preferably 12 to 30 mgKOH / g, more preferably 15 to 28 mgKOH / g, and 20 to 27 mgKOH / g from the viewpoint of obtaining an excellent cured film. Further preferred.
  • the amine value of the polyamine dispersant (B) is preferably 7 to 45 mgKOH / g, more preferably 8 to 44 mgKOH / g, and more preferably 20 to 43 mgKOH / g from the viewpoint of obtaining an excellent cured film. g is more preferable, and 30 to 42 mgKOH / g is particularly preferable.
  • the polyamine dispersant is preferably a graft polymer having a main chain of polyamine and / or polyimine and a side chain of polyester.
  • polyamine that is the main chain of the graft polymer examples include polyallylamine, poly (n-alkyl) allylamine, and polyvinylamine.
  • polyimine that is the main chain examples include polymers of alkyleneimines having 2 to 6 carbon atoms. Can be mentioned.
  • the polyimine is preferably poly (C 2-4 alkyleneimine), more preferably polyethyleneimine.
  • the main chain polyamine and / or polyimine may be a straight chain, but is preferably a branched chain, and has an appropriate molecular weight from various commercially available products according to the desired physical properties. Can be selected and used.
  • the weight average molecular weight of the polyamine and / or polyimine is preferably from 300 to 10,000, and more preferably from 500 to 5,000.
  • the polyester as the side chain is obtained by reacting a hydroxycarboxylic acid or lactone with a carboxylic acid (eg, acetic acid, caproic acid, lauric acid, etc.) in the presence of an esterification catalyst (eg, tetrabutyl titanate, zirconium naphthenate, zinc acetate, etc.). It can be prepared by heat polymerization at ⁇ 200 ° C.
  • carboxylic acid eg, acetic acid, caproic acid, lauric acid, etc.
  • an esterification catalyst eg, tetrabutyl titanate, zirconium naphthenate, zinc acetate, etc.
  • hydroxycarboxylic acid examples include saturated or unsaturated hydroxycarboxylic acids having 8 to 20 carbon atoms, preferably 14 to 20 carbon atoms. Preferred examples thereof include ⁇ -hydroxystearic acid, 12-hydroxystearic acid, Examples thereof include 10-hydroxystearic acid and ricinoleic acid.
  • the main chain is preferably polyallylamine or polyethyleneimine
  • the side chain is preferably a polyester having a polymer of ⁇ -hydroxystearic acid or 12-hydroxystearic acid or a ring-opening polymer of lactone, More preferably, the main chain is a polyethyleneimine and the side chain is a polyester having a polymer of ⁇ -hydroxystearic acid or 12-hydroxystearic acid.
  • polyamine dispersant those described in, for example, Japanese Patent No. 1940521, Japanese Patent No. 1570685, Japanese Patent No. 3504268, Japanese Patent Publication No. 2003-509205, and the like can be used.
  • Solsperse 24000GR manufactured by Nippon Lubrizol Co., Ltd.
  • Solsperse 24000SC (acid value 25 mgKOH / g, amine value 40 mgKOH / g), 32000 (acid value 15 mgKOH / g, amine value 30 mgKOH / g), 33000 (acid value 26 mgKOH / g) Ajinomoto Fine Techno Co., Ltd.
  • PB-821 (acid value 17 mgKOH / g, amine value 10 mgKOH / g, main chain: polyallylamine, side chain: polycaprolactone), PB -822 (acid value 12 mg KOH / g, amine value 17 mgKOH / g), PB-824 (acid value 21 mgKOH / g, amine value 17 mgKOH / g), PB-827 (acid value 13 mgKOH / g, amine value 17 mgKOH / g), PB- 881 (acid value 17 mgKOH / g, amine value 17 mgKOH / g) and the like.
  • the optical functional layer according to the present invention preferably contains an aluminum chelating agent and further a titanium chelating agent from the viewpoint of improving weather resistance.
  • Examples of the aluminum chelating agent useful in the present invention include aluminum tris (ethyl acetoacetate), aluminum tris (methyl acetoacetate), aluminum tris (sec-butyl acetoacetate), aluminum tris (hexyl acetoacetate), aluminum tris ( iso-octyl acetoacetate), aluminum ethyl acetoacetate diisopropylate, aluminum butyl acetoacetate diisopropylate, aluminum hexyl acetoacetate diisopropylate, aluminum octyl acetoacetate diisopropylate, aluminum ethyl acetoacetate hexylate isopropylate, aluminum Hexyl acetoacetate diisobutyrate, aluminum benzyl acetate DOO acetate diisopropylate and the like.
  • the addition amount is preferably 10 to 120% by mass, more preferably 40 to 110% by mass, based on the content of the vanadium dioxide-containing particles. When it is 10% by mass or more, desired weather resistance can be obtained, and when it is 120% by mass or less, the particles can be mixed into the coating liquid without agglomeration.
  • the aluminum chelating agent according to the present invention is preferably a compound having a partial structure represented by the following chemical formula (A).
  • ALCH aluminum ethylacetate
  • Acetate diisopropylate is preferred.
  • the optical functional layer according to the present invention preferably further contains a titanium chelating agent from the viewpoint of further improving the weather resistance.
  • Titanium chelating agents include titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium octylene glycolate, titanium phosphate compound, titanium lactate, titanium triethanolamate, titanium lactate ammonium salt, titanium octylene.
  • examples include glycolate compounds, titanium-1,3-propanedioxybis (ethylacetoacetate), titanium dodecylbenzenesulfonate compounds, titanium diethanolamate, and titanium aminoethylaminoethanolate.
  • the amount of these titanium chelates used is preferably 20 to 300% by mass with respect to the vanadium dioxide-containing particles. Within this range, haze and weather resistance are good.
  • Multifunctional thiol As the polyfunctional thiol that can be used in the present invention, any appropriate kind of polyfunctional thiol can be adopted depending on the purpose. Only one type of polyfunctional thiol may be used, or two or more types may be used in combination.
  • the addition amount is preferably 10 to 120% by mass, more preferably 10 to 100% by mass, based on the content of the vanadium dioxide-containing particles. When it is 10% by mass or more, desired weather resistance can be obtained, and when it is 120% by mass or less, the particles can be mixed into the coating liquid without agglomeration.
  • any appropriate polyfunctional thiol can be adopted as long as it is a compound having two or more mercapto groups in one molecule.
  • the polyfunctional thiol is preferably a thiol compound having a specific mercapto group-containing group, wherein the mercapto group-containing group has a carbon atom at the ⁇ -position and / or ⁇ -position with respect to the mercapto group (—SH). It is a structure having a substituent. At least one of the substituents is preferably an alkyl group.
  • the above “structure in which the carbon atom at the ⁇ -position and / or ⁇ -position with respect to the mercapto group (—SH) has a substituent” means a structure branched at the carbon at the ⁇ -position and / or ⁇ -position with respect to the mercapto group, That is, it means a so-called branched structure in which the ⁇ -position and / or ⁇ -position carbon of the mercapto group is bonded to three or more atoms other than hydrogen.
  • At least one of the substituents is an alkyl group
  • at least one of the substituents other than the main chain at the ⁇ -position and / or the ⁇ -position with respect to the mercapto group is an alkyl group.
  • the “main chain” means the longest chain structure composed of atoms other than hydrogen containing a mercapto group.
  • the mercapto group-containing group is preferably a group represented by the general formula (1).
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which is an alkyl group. That is, R 1 and R 2 are not both hydrogen atoms. In addition, when both R 1 and R 2 are alkyl groups, they may be the same or different.
  • m is 0 or an integer of 1 to 2, preferably 0 or 1, and n is 0 or 1, preferably 0.
  • the alkyl group having 1 to 10 carbon atoms that can be adopted by R 1 and R 2 may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group.
  • it is a methyl group or an ethyl group.
  • the polyfunctional thiol is more preferably a carboxylic acid derivative structure such that the mercapto group-containing group represented by the general formula (1) is represented by the following general formula (2).
  • Such a polyfunctional thiol is preferably an ester of a mercapto group-containing carboxylic acid represented by the following general formula (3) and an alcohol.
  • polyfunctional alcohols are preferable.
  • Examples of the polyfunctional alcohol include alkylene glycol (however, the alkylene group preferably has 2 to 10 carbon atoms, and the carbon chain may be branched), diethylene glycol, glycerin, dipropylene glycol, trimethylol. Examples include propane, pentaerythritol, and dipentaerythritol. Examples of the alkylene glycol include ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and tetramethylene glycol.
  • the polyfunctional alcohol is preferably alkylene glycol having 2 carbon atoms in the alkylene main chain such as ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, and trimethylolpropane.
  • Examples of the mercapto group-containing carboxylic acid represented by the general formula (2) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 2-mercaptoisobutyric acid, and 3-mercaptoisobutyric acid.
  • polyfunctional thiol having the structure of the general formula (1) include the following compounds.
  • hydrocarbon dithiol examples include 2,5-hexanedithiol, 2,9-decanedithiol, and 1,4-bis (1-mercaptoethyl) benzene.
  • Examples of the compound having an ester bond structure include di (1-mercaptoethyl ester) phthalate, di (2-mercaptopropyl ester) phthalate, di (3-mercaptobutyl ester) phthalate, and di (3-mercapto phthalate). Isobutyl ester).
  • polyfunctional thiol having the structure of the general formula (1) preferably, for example, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis- (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), tri Methylolethane tris (3-mercaptobutyrate), butanediol bisthioglycolate (BDTG), hexanediol bisthioglycolate (HDTG), trimethylolpropane tristhioglycolate (TMTG), pentaerythritol tetrakisthioglycolate (PETG) ), Ethylene glycol biscuit Propionate (EGTP), butane
  • any appropriate molecular weight can be adopted as the molecular weight of the polyfunctional thiol. Preferably it is 200-1000.
  • any appropriate production method can be adopted as the production method of the polyfunctional thiol.
  • an ester of a mercapto group-containing carboxylic acid and an alcohol is obtained by reacting the mercapto group-containing carboxylic acid represented by the general formula (2) and an alcohol according to a conventional method to form an ester.
  • a conventional method to form an ester.
  • about the conditions of ester reaction it can select suitably from arbitrary appropriate reaction conditions.
  • any appropriate commercially available product may be used as the polyfunctional thiol.
  • “Karenz MT” series manufactured by Showa Denko KK specifically, for example, “Karenz MT BD1”, “Karenz MT NR1”, and “Karenz MT PE1” can be mentioned.
  • Substrate The substrate applicable to the present invention is preferably transparent, and examples thereof include glass, quartz, and a transparent resin film. However, flexibility and production suitability (manufacturing process suitability) can be mentioned. ) Is preferably a transparent resin film.
  • “transparent” 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. is there.
  • the thickness of the 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 substrate is 30 ⁇ m or more, wrinkles and the like are less likely to occur during handling, and if it is 200 ⁇ m or less, for example, when making a laminated glass, follow the curved surface of the glass when bonded to the glass substrate. Sexuality improves.
  • the 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.
  • a stretched film is more preferable when the laminated glass provided with the thermochromic film of the present invention is used as an automobile windshield.
  • the base material preferably has a thermal shrinkage within the range of 0.1 to 3.0% at a temperature of 150 ° C. from the viewpoint of preventing the formation and cracking of the thermochromic film. More preferably, it is within the range of 0.0%.
  • the 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 films for example, polyethylene terephthalate, polyethylene naphthalate, etc.
  • triacetyl cellulose films and the like.
  • polyester film (hereinafter simply referred to as “polyester”) is not particularly limited, but includes polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, terephthalic acid and 2,6-naphthalenedicarboxylic acid, Polyesters composed mainly of a copolymerized polyester composed of ethylene glycol and a mixture of two or more of these polyesters are preferred.
  • particles may be contained 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 transparent resin film may be subjected to relaxation treatment or offline heat treatment in terms of dimensional stability.
  • the relaxation treatment is performed in a process from the heat setting in the stretch film forming step of the polyester film to the winding in the transverse stretch tenter or after exiting the tenter.
  • the relaxation treatment is preferably carried out at a treatment temperature in the range of 80 to 200 ° C, more preferably in the range of 100 to 180 ° C.
  • the relaxation rate is preferably in the range of 0.1 to 10% in both the longitudinal direction and the width direction, and more preferably in the range of 2 to 6%.
  • the relaxed substrate is subjected to off-line heat treatment to improve heat resistance and further improve dimensional stability.
  • the transparent resin film is preferably coated with an undercoat layer coating solution inline on one or both sides during the film formation process.
  • undercoating during the film forming process is referred to as in-line undercoating.
  • thermochromic film of the present invention may be provided with a hard coat layer (also referred to as HC layer) in order to improve the durability of the film.
  • a hard coat layer also referred to as HC layer
  • an inorganic material typified by polysiloxane, an active energy ray curable resin, or the like can be used.
  • the inorganic material needs to be moisture-cured (from room temperature to warming), and it is preferable to use an active energy ray-curable resin from the viewpoint of curing temperature, curing time, and cost.
  • the active energy ray resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams.
  • the active energy ray curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin layer is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. It is formed.
  • an active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.
  • the ultraviolet curable resin examples include an ultraviolet curable acrylate resin, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable resin.
  • a type epoxy resin or the like is preferably used. Of these, ultraviolet curable acrylate resins are preferred.
  • the ultraviolet curable acrylate resin polyfunctional acrylate is preferable.
  • the polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate.
  • the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.
  • polyfunctional acrylate monomer examples include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate.
  • monofunctional acrylate may be used.
  • Monofunctional acrylates include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, lauryl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl Examples thereof include acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and cyclohexyl acrylate.
  • Such monofunctional acrylates can be obtained from Nippon Kasei Kogyo Co., Ltd., Shin-Nakamura Chemical Co., Ltd., Osaka Organic Chemical Co., Ltd., etc.
  • monofunctional acrylate 80: 20 to 100: 0 in terms of mass ratio of polyfunctional acrylate and monofunctional acrylate.
  • the UV curable urethane acrylate resin generally includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in addition to a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It is easily obtained by reacting an acrylate monomer having a hydroxy group such as 2-hydroxypropyl acrylate.
  • acrylate 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate
  • acrylate 2-hydroxyethyl methacrylate
  • An ultraviolet curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid with a hydroxyl group or carboxy group at the end of the polyester (see, for example, JP Sho 59-151112).
  • An ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.
  • ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipenta.
  • examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.
  • Toning layer in order to adjust the color of the thermochromic film, a toning layer containing a dye or pigment having a maximum absorption wavelength in the range of 350 to 750 nm may be provided. Good.
  • “Dye” refers to a dye that is used as a coloring material and dissolves in any solvent such as water or an organic solvent. “Pigment” refers to a pigment that is used as a coloring material to be colored and is in the form of a fine powder of a pigment that does not dissolve in water or an organic solvent.
  • the dye having a maximum absorption wavelength within the light wavelength range of 350 to 750 nm that can be used in the present invention include anthraquinone dyes, phthalocyanine dyes, triphenylmethane dyes, triarylmethane dyes, and indigo dyes. And pigments.
  • a compound classified as “Pigment” in the color index (CI; issued by The Society of Dyersand Colorists) can be used, and phthalocyanine-based C.I. I. Pigment blue 15: 3 (maximum absorption wavelength: 630 nm, 720 nm), C.I. I. Pigment Blue 15: 4 (maximum absorption wavelength: 640 nm, 740 nm), C.I. I. Pigment Blue 16 (maximum absorption wavelength: 620 nm, 690 nm) or the like can be preferably used.
  • thermochromic composite includes a thermochromic composite including a thermochromic film.
  • the thermochromic film of the present invention can be used after being pasted on glass.
  • the glass which bonded the thermochromic film can be used for a motor vehicle, a rail vehicle, an aircraft, a ship, a building, etc., it does not restrict
  • thermochromic composite composed of a thermochromic film support including glass and a thermochromic film.
  • thermochromic film of this invention it can be used as a thermochromic composite body provided with the thermochromic film as a component.
  • FIG. 3 is a schematic cross-sectional view showing an example of the configuration of the thermochromic complex provided with the thermochromic film of the present invention.
  • thermochromic composite 7 of the present invention is configured by bonding the thermochromic film 1 of the present invention to a glass member 6 with an adhesive layer 5.
  • a polyethylene terephthalate (PET) film which is a transparent substrate 2 constituting the thermochromic film 1 on the glass member 6 with an adhesive layer 5 interposed therebetween,
  • An optical functional layer 3 is disposed on the PET film, a PET film that is a transparent substrate 2 thereon, and a hard coat layer 4 is disposed on the outermost layer.
  • laminated glass In the case of laminated glass, it can be used for automobiles, railway vehicles, aircraft, ships and buildings. 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. In particular, since alkali components derived from glass are considered to inhibit thermochromic properties, alkali-free glass is more preferable.
  • thermochromic film support including glass and a thermochromic
  • 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, 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 50 ⁇ m, more preferably 3 to 30 ⁇ 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 50 ⁇ m or less, not only the transparency of the thermochromic film is improved, but also when the thermochromic film is attached to the window glass and then peeled off, cohesive failure does not occur between the adhesive layers, and adhesion to the glass surface There is a tendency that there is no remaining agent.
  • additives can be added to the pressure-sensitive adhesive, and preferably an ultraviolet absorber and an antioxidant can be contained.
  • thermochromic film 101 to 117 were produced as follows.
  • a raw material liquid container (105) 19.0 g of vanadium oxide sulfate (IV) (VOSO 4 ) was dissolved in ion exchange water (dissolved oxygen amount: 8.1 mg / L) in a raw material liquid container (105) to 300 mL, and this liquid was stirred. Then, 68 mL of a 3.0 mol / L NH 3 aqueous solution was added as an alkali to prepare a raw material liquid 1 having a pH of 8.0 (liquid temperature: 25 ° C.).
  • ion exchange water (dissolved oxygen amount: 8.1 mg / L) was stored as the raw material liquid 2 in the raw material liquid container (102).
  • a raw material liquid 1 containing vanadium oxide (IV) sulfate and an alkali is fed from a raw material liquid container (105) through a flow path (106) by a pump (107), and heated by a heating medium (115) at 25 ° C. and 30 MPa.
  • the pressure was applied to satisfy the following conditions.
  • the ion exchange water as the raw material liquid 2 is fed from the raw material liquid container (102) through the flow path (103) by the pump (104), and is heated by the heating medium (113) at 440 ° C. and 30 MPa. Supercritical water was obtained by heating and pressing.
  • a raw material liquid 1 containing vanadium oxide (IV) sulfate and an alkali and a raw material liquid 2 that is supercritical water at a confluence point MP under the condition that the raw material liquid 1: the raw material liquid 2 1: 4.
  • a reaction solution 1 was prepared and fed to the hydrothermal reaction section (116).
  • the reaction liquid 1 was sent to the heating part piping (117) arrange
  • the treatment time (passage time) was 2 seconds under the conditions of 400 ° C. and 30 MPa, and vanadium dioxide (VO 2 ) -containing particles were formed.
  • the reaction liquid 1 was cooled in the cooling part (108), and the dispersion liquid containing vanadium dioxide containing particle
  • the obtained product is washed using ultrafiltration, and dispersed with a super apex mill manufactured by Kotobukisha using zirconia beads having a particle diameter of 30 ⁇ m to prepare an aqueous dispersion of vanadium dioxide-containing particles. did.
  • the vanadium dioxide particles with different dispersion times were sampled to measure the number average particle diameter, thereby obtaining vanadium dioxide-containing particle solvent dispersions having number average particle diameters of 30 nm, 50 nm, 100 nm, 200 nm, and 300 nm, respectively. It was.
  • a particle size measurement sample was prepared by mixing the vanadium dioxide-containing particle solvent dispersion with a solvent so that the concentration was 0.01% by mass.
  • the number average particle size (nm) of the sample for particle size measurement was measured with a dynamic light scattering analyzer.
  • Formation of optical functional layer 1 On a polyethylene terephthalate film (Toyobo A4300, double-sided adhesive layer) having a thickness of 50 ⁇ m, the thickness after drying the coating solution 1 for forming an optical functional layer prepared by the following method using an extrusion coater is 1.5 ⁇ m. The coating amount was adjusted so that the wet coating was performed, and warm air at 90 ° C. was blown for 1 minute to dry to form the optical functional layer 1, thereby producing a thermochromic film 101.
  • ⁇ Preparation of coating solution 1 for forming an optical functional layer> The following constituent materials were sequentially added, mixed and dissolved, and diluted with methyl isobutyl ketone so as to have a solid content of 20% by mass to prepare a coating solution 1 for forming an optical functional layer.
  • thermochromic film 101 Vanadium dioxide-containing particle solvent dispersion (number average particle size 30 nm) 13 parts by mass Binder resin (Acrylic resin: DIC Corporation Acrydic B L-616) 87 parts by mass [Preparation of Thermochromic Film 102]
  • a thermochromic film 102 was produced in the same manner except that the vanadium dioxide-containing particles used in the optical functional layer were changed to vanadium dioxide-containing particles having a number average particle diameter of 50 nm.
  • thermochromic film 101 a thermochromic film 103 was produced in the same manner except that the vanadium dioxide-containing particles used in the optical functional layer were changed to vanadium dioxide-containing particles having a number average particle diameter of 100 nm.
  • thermochromic film 104 was produced in the same manner as in the production of the thermochromic film 101 except that the vanadium dioxide-containing particles used in the optical functional layer were changed to vanadium dioxide-containing particles having a number average particle diameter of 200 nm.
  • thermochromic film 105 In the production of the thermochromic film 101, a thermochromic film 105 was produced in the same manner except that the vanadium dioxide-containing particles used in the optical functional layer were changed to vanadium dioxide-containing particles having a number average particle diameter of 300 nm.
  • thermochromic film 106 was prepared in the same manner except that the vanadium dioxide-containing particles used were vanadium dioxide-containing particles doped with 0.5 at% (atomic concentration) of tungsten (W) on the particle surface. was made.
  • thermochromic film 107 an optical functional layer was formed on the substrate in the same manner except that the polymer dispersant was changed to PA-075F (polymer polyamine type) manufactured by NOF Corporation, and the thermochromic film was formed. 107 was produced. PA-075F was added in an amount of 10% by mass with respect to the vanadium dioxide-containing particles.
  • thermochromic film 106 was prepared in the same manner except that the binder resin was changed to a polyfunctional acrylate compound: Aronix M-313 manufactured by Toagosei Co., Ltd. and the following coating solution 2 for forming an optical functional layer was used. A chromic film 108 was produced.
  • thermochromic film 109 W-doped vanadium dioxide-containing particle solvent dispersion (number average particle size 50 nm 13 parts by weight Binder resin (acrylic resin: Aronix M-3 manufactured by Toa Gosei Co., Ltd.) 13) 84 parts by mass Irgacure 184 (manufactured by BASF Japan Ltd.) 3 parts by mass [Preparation of thermochromic film 109]
  • an aluminum chelating agent Algomer 800AF manufactured by Kawaken Fine Chemical Co., Ltd.
  • thermochromic film 110 W-doped vanadium dioxide-containing particle solvent dispersion (number average particle size 50 nm 13 parts by weight Binder resin (acrylic resin: Aronix M-3 manufactured by Toa Gosei Co., Ltd.) 13) 74 parts by mass Aluminum chelating agent (Algomer 8 manufactured by Kawaken Fine Chemical Co., Ltd.) 00F) 10 parts by mass Irgacure 184 (manufactured by BASF Japan Ltd.) 3 parts by mass [Preparation of Thermochromic Film 110] In producing the thermochromic film 109, the thermochromic film 110 was similarly used except that an aluminum chelating agent (ALM: aluminum alkyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.) was used instead of the Algomer 800AF. Was made.
  • ALM aluminum alkyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.
  • thermochromic film 111 In producing the thermochromic film 109, the thermochromic film 111 was similarly used except that an aluminum chelating agent (ALCH: aluminum ethyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.) was used in place of the Algomer 800AF in the same mass part. Was made.
  • ALCH aluminum ethyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.
  • thermochromic film 112 In the production of the thermochromic film 111, a thermochromic film 112 was produced in the same manner except that a titanium chelating agent (TC-750 manufactured by Matsumoto Fine Chemical Co., Ltd.) was added and the following coating solution 4 for forming an optical functional layer was used. did.
  • a titanium chelating agent TC-750 manufactured by Matsumoto Fine Chemical Co., Ltd.
  • thermochromic film 112 25 parts by mass Irgacure 184 (manufactured by BASF Japan Ltd.) 2 parts by mass
  • thermochromic film 112 a polyfunctional thiol (Karenz MT @ BD1 manufactured by Showa Denko KK) was further added, and the thermochromic film 113 was formed in the same manner except that the following coating solution 5 for forming an optical functional layer was used. Produced.
  • thermochromic film 114 was produced in the same manner except that the polyfunctional thiol was changed to butanediol bisthioglycolate (BDTG) in the production of the thermochromic film 113.
  • BDTG butanediol bisthioglycolate
  • thermochromic film 115 In the production of the thermochromic film 114, the binder resin was replaced with Aronix M-305 manufactured by Toa Gosei Co., Ltd. which is a polyfunctional pentaerythritol (meth) acrylate compound, except that the following coating solution 6 for forming an optical functional layer was used. In the same manner, a thermochromic film 115 was produced.
  • thermochromic film 115 25 parts by mass Irgacure 184 (manufactured by BASF Japan Ltd.) 2 parts by mass polyfunctional thiol (BDTG) 10 parts by mass [of thermochromic film 116 Production)
  • an optical functional layer was formed on the substrate in the same manner except that the polymer dispersant was changed to PA-085C (polymer polyamine type) manufactured by NOF Corporation, and the thermochromic film was formed. 116 was produced.
  • PA-085C was added in an amount of 10% by mass with respect to the vanadium dioxide-containing particles.
  • thermochromic film 117 In the production of the thermochromic film 102, a thermochromic film 117 of a comparative example was produced in the same manner except that the polymer dispersant was not added.
  • thermochromic film 101 to 117 were evaluated as follows.
  • the prepared particle size measurement sample was subjected to a hydrodynamic diameter by a dynamic light scattering (Dynamic Light Scattering, DLS) method using a dynamic light scattering analyzer (DLS-8000, manufactured by Otsuka Electronics Co., Ltd.). (Nm) was measured. Based on this, the number average particle size of the particle size distribution by cumulant analysis was determined.
  • DLS Dynamic Light Scattering
  • thermochromic film wet heat resistance>
  • transmission using a spectrophotometer manufactured by JASCO Corporation, V-670
  • ⁇ E color difference
  • ⁇ VLT visible light transmittance difference
  • thermochromic films (Color difference) A: ⁇ E ⁇ 2 ⁇ : 2 ⁇ E ⁇ 3 ⁇ : 3 ⁇ E ⁇ 4 ⁇ : 4 ⁇ ⁇ E (Visible light transmittance difference) A: ⁇ VLT ⁇ 2 ⁇ : 2 ⁇ VLT ⁇ 3 ⁇ : 3 ⁇ VLT ⁇ 4 ⁇ : 4 ⁇ ⁇ VLT (Haze difference) ⁇ : ⁇ haze ⁇ 3% ⁇ : 3% ⁇ haze ⁇ 4% X: 4% ⁇ ⁇ Haze Table I and Table II show the structures and evaluation results of the above thermochromic films.
  • thermochromic films 101 to 116 having the constitution of the present invention are excellent in haze and weather resistance immediately after the comparative example.
  • thermochromic films 113 to 116 in which the preferred acrylic resin, polymer dispersant, chelating agent and polyfunctional thiol were added to the optical functional layer were excellent in each characteristic.
  • Example 2 Each thermochromic film produced in Example 1 was made into a transparent adhesive sheet (manufactured by Nitto Denko Corporation, LUCIACS) with 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”) When a thermochromic film-glass composite was produced by bonding using CS9621T), the same effect could be confirmed.
  • thermochromic film of the present invention suppresses haze rise and is excellent in weather resistance, so it can be used after being pasted on glass, and can be used for automobiles, railway vehicles, aircraft, ships, buildings, etc. . Specifically, it can be preferably used for window glass for construction, rear glass for vehicles, roof glass and the like.
  • Thermochromic film 1 Thermochromic film 2 Base material) DESCRIPTION OF SYMBOLS 3 Optical function layer 4 Hard-coat layer 5 Adhesion layer 6 Glass 7 Thermochromic complex 101 Flow-type reaction apparatus 102, 105 Raw material liquid container 103, 106, 111, 118 Flow path (pipe) 104, 107, 112 Pump 108 Cooling unit 109, 110 Tank 113, 114, 115 Heating medium 116 Hydrothermal reaction unit 117 Heating unit piping 119 Control valve B Acrylic resin VO S Vanadium dioxide-containing primary particles VO M Vanadium dioxide-containing secondary Particle C Refrigerant IN Heating medium inlet OUT Heating medium outlet L Heater piping line length MP Junction point TC Temperature sensor

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

La présente invention aborde le problème de la fourniture d'un film thermochromique et d'un corps composite de film thermochromique, qui sont supprimés en augmentant le trouble, tout en ayant une excellente résistance aux intempéries. Un film thermochromique selon la présente invention comprend, sur un substrat, au moins une couche fonctionnelle optique qui contient des particules contenant du dioxyde de vanadium qui présentent des propriétés thermochromiques; et ce film thermochromique est caractérisé en ce que la couche fonctionnelle optique contient en outre une résine acrylique et un dispersant polymère.
PCT/JP2018/006106 2017-03-10 2018-02-21 Film thermochromique et corps composite à film thermochromique Ceased WO2018163809A1 (fr)

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JP2007178915A (ja) * 2005-12-28 2007-07-12 Fujifilm Corp 金属微粒子分散物及び赤外線遮蔽フィルター
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JP7302957B2 (ja) 2018-09-25 2023-07-04 日本クロージャー株式会社 示温性プラスチック容器蓋

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