Electrochromic element and eyeglass lens

Abstract

The purpose of the present invention is to provide: an electrochromic element in which deterioration of responsiveness is suppressed by causing a layered structure to have a gas barrier property; and a spectacle lens. This electrochromic element (10) is formed by layering a support body (1) and an electrochromic film (2) in which electrode layers (5, 6) and an electrochromic layer (7) are included. The electrochromic element is characterized by the layered structure constituting the electrochromic element being layered by a barrier layer (11). Is it preferrable for the barrier layer (11) to have transparency and the gas barrier property.

Description

[Technical Field]

[0001] The present invention relates to an electrochromic element capable of reversibly controlling color development and fading by electricity, and to an eyeglass lens. [Background technology]

[0002] Electrochromic elements, which utilize the electrochromism phenomenon in which a reversible oxidation-reduction reaction occurs when a voltage is applied, thereby reversibly changing color, are used, for example, as eyeglass lenses. Patent Document 1 discloses an electrochromic element in which a pair of substrates and an electrode layer and an electrochromic layer disposed between the substrates are stacked. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-111389 Summary of the Invention [Problem to be solved by the invention]

[0004] An electrochromic element is an element that utilizes the electrochromism phenomenon, which causes a reversible oxidation-reduction reaction by applying a voltage to both electrodes, thereby causing a reversible change in color.

[0005] However, there is a problem that the response is reduced due to the intrusion of moisture or oxygen from the front or back surface of the electrochromic element.

[0006] The present invention has been made to solve the above problems, and aims to provide an electrochromic element and an eyeglass lens in which the laminate structure has gas barrier properties and the decrease in responsiveness is suppressed. [Means for solving the problem]

[0007] The electrochromic device of the present invention comprises a support and a pair Electrode layer and provided between the pair of electrode layers and an electrochromic film having an electrochromic layer, wherein a barrier layer is laminated on the laminate structure constituting the electrochromic element, and the electrochromic film is formed by laminating a pair of substrates and the a pair The above laminated between the substrates a pair The electrochromic layer is provided between the pair of substrates, and a sealing layer is provided around the electrochromic layer. The barrier layer is provided between the pair of substrates. base Board and The pair Between the electrode layer , respectively The sealing layer also has gas barrier properties.

[0008] In the present invention, the barrier layer preferably has transparency as well as gas barrier properties.

[0009] Book In the invention, the barrier layer is Furthermore, It may be configured to be disposed between the support and the electrochromic film.

[0010] Book The eyeglass lens of the present invention is the electrochromic element described above, characterized in that the support is a lens substrate. [Effects of the Invention]

[0011] According to the electrochromic element of the present invention, the laminated structure is provided with a barrier layer, which can improve the gas barrier properties and provide excellent response. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a cross-sectional view illustrating an electrochromic element according to a first embodiment of the present invention. [Figure 2] FIG. 4 is a cross-sectional view illustrating an electrochromic element according to a second embodiment of the present invention. [Figure 3] FIG. 10 is a cross-sectional view illustrating an electrochromic element according to a third embodiment of the present invention. [Figure 4] 3A to 3C are explanatory diagrams showing a manufacturing process of an electrochromic element according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, an embodiment of the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail.

[0014] <Conventional Issues with Electrochromic Elements and Outline of the Present Embodiment> Electrochromic elements are elements that utilize the phenomenon of electrochromism, which causes a reversible oxidation-reduction reaction by applying a voltage to both electrodes, resulting in a reversible color change. For example, electrochromic elements can be used as eyeglass lenses, functioning as sunglasses in bright places and as clear lenses in dark places. They can be switched on or automatically adjusted to the optimum brightness.

[0015] The electrochromic element has a laminated structure in which an electrochromic film having an electrode layer and an electrochromic layer is laminated on the surface of a support.

[0016] However, if moisture or oxygen penetrates from the front or back of the electrochromic element through the laminated structure to the electrochromic layer, there is a problem in that the reversibility of the oxidation-reduction reaction decreases, and the responsiveness of the color change due to the electrochromism phenomenon decreases.

[0017] Therefore, as a result of intensive research, the inventors have found that by disposing a barrier layer in the laminated structure that constitutes the electrochromic element, it is possible to suppress the penetration of moisture and oxygen into the laminated layer and improve the responsiveness. The layer structure of the electrochromic element in this embodiment will be specifically described below.

[0018] <Electrochromic Element 10 in First Embodiment> FIG. 1 is a schematic cross-sectional view of an electrochromic device 10 according to a first embodiment of the present invention. The electrochromic device 10 is configured to include a support 1 and an electrochromic film 2 laminated on the surface of the support 1.

[0019] [Support 1] The support 1 is required to be transparent and have high transmittance. The material of the support 1 is not limited, but examples thereof include a moldable resin substrate such as polycarbonate resin, acrylic resin, epoxy resin, or phenolic resin, or a glass substrate. Of these, it is preferable that the support 1 be made of polycarbonate resin from the viewpoints of moldability and manufacturing costs.

[0020] [Electrochromic Film 2] The electrochromic film 2 includes a pair of a first substrate 3 and a second substrate 4, a pair of a first electrode layer 5 and a second electrode layer 6 provided on the inner surfaces of the first substrate 3 and the second substrate 4, and an electrochromic layer 7 provided between the first electrode layer 5 and the second electrode layer 6. The electrochromic layer 7 includes a reduction layer 7a disposed on the first electrode layer 5 side, an oxidation layer 7b disposed on the second electrode layer 6 side, and an electrolyte layer 7c provided between the reduction layer 7a and the oxidation layer 7b. As such, the electrochromic film 2 is stacked in the following order from the bottom in FIG. 1: second substrate 4 / second electrode layer 6 / oxidation layer 7b / electrolyte layer 7c / reduction layer 7a / first electrode layer 5 / first substrate 3.

[0021] The substrates 3 and 4 constituting the electrochromic film 2 are in the form of a film or sheet and can be formed from the same resin material as the support 1. Like the support 1, the substrates 3 and 4 are also required to be transparent and have high transmittance. Like the support 1, the substrates 3 and 4 are preferably formed from a polycarbonate resin.

[0022] The electrode layers 5 and 6 constituting the electrochromic film 2 are required to have transparency, high transmittance, and excellent conductivity. To satisfy these characteristics, the electrode layers 5 and 6 are transparent electrode layers, and ITO (indium tin oxide) is particularly preferably used. The reduction layer 7a, the oxidation layer 7b, and the electrolyte layer 7c that constitute the electrochromic layer 7 can be made of existing materials.

[0023] The reduction layer 7a is a layer that develops color as a result of a reduction reaction. Existing reduction-type electrochromic compounds can be used for the reduction layer 7a. Whether organic or inorganic, the reduction layer 7a may be made of, but is not limited to, azobenzenes, anthraquinones, diarylethenes, dihydroprenes, dipyridines, styryls, styrylspiropyrans, spirooxazines, spirothiopyrans, thioindigo compounds, tetrathiafulvalenes, terephthalic acid compounds, triphenylmethanes, triphenylamines, naphthopyrans, viologens, pyrazolines, phenazines, phenylenediamines, phenoxazines, phenothiazines, phthalocyanines, fluorans, fulgides, benzopyrans, metallocenes, tungsten oxide, molybdenum oxide, iridium oxide, and titanium oxide.

[0024] The oxidation layer 7b is a layer that develops color as a result of an oxidation reaction. Existing oxidation-type electrochromic compounds can be used for the oxidation layer 7b. The material may be organic or inorganic, and may be selected from, but is not limited to, a composition containing a radical polymerizable compound having triarylamine, a Prussian blue complex, nickel oxide, iridium oxide, and the like.

[0025] The electrolyte layer 7c preferably has electronic insulation and ionic conductivity, and is also transparent. The electrolyte layer 7c may be a solid electrolyte, a gel, a liquid, or the like. A gel is preferable to maintain high ionic conductivity. Existing electrolyte materials may be used, but are not limited to, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids, and the like.

[0026] [Functional Layer 15] As shown in FIG. 1, a functional layer 15 including, for example, a hard coat layer 12, an anti-reflection layer 13, and a water-repellent layer 14 is provided on the surface of the electrochromic film 2.

[0027] The hard coat layer 12 can impart scratch resistance to the electrochromic element 10. The hard coat layer 12 is made of a curable composition, and examples of the curable composition that can be preferably used include a photocurable silicone composition, an acrylic ultraviolet-curable monomer composition, and a thermosetting composition containing inorganic fine particles such as SiO2 or TiO2.

[0028] The anti-reflection layer 13 is typically a multilayer structure in which layers with different refractive indices are stacked, and is a film that prevents light reflection through interference. The anti-reflection layer 13 has a structure in which low-refractive-index layers and high-refractive-index layers are alternately stacked. While not limited thereto, it is preferable to use SiO2 for the low-refractive-index layers. Furthermore, ZrO2, Y2O3, Al2O3, etc. can be used for the high-refractive-index layers. For example, a fluorine-based substance can be preferably used for the water-repellent layer 14. The water-repellent layer 14 preferably has not only water-repellent properties but also antibacterial properties. The functional layer 15 can be configured to include at least one layer selected from the group consisting of a hard coat layer 12, an anti-reflection layer 13, an anti-static layer, a water-repellent layer 14, and an anti-fogging layer.

[0029] [Sealing layer 16] As shown in Fig. 1, a sealing layer 16 is provided between the first substrate 3 and the second substrate 4 and around the electrochromic layer 7. As shown in Fig. 1, parts of the first electrode layer 5 and the second electrode layer 6 extend to the position of the sealing layer 16, and metal terminal portions 17 are formed on each of the electrode layers 5, 6. The metal terminal portions 17 are exposed to the outside, and a voltage can be applied between the pair of electrode layers 5, 6 through the metal terminal portions 17.

[0030] [Barrier layer 11] The barrier layer 11 will now be described. In the first embodiment shown in FIG.

[0031] The barrier layer 11 preferably has gas barrier properties and transparency. The gas barrier properties can be evaluated by the water vapor transmission rate (WVTR) and O2 transmission rate. The gas barrier properties can be measured using the Lyssy method, the MOCON method, gas chromatography, API-MS, Ca corrosion method, and differential pressure method. For example, the water vapor transmission rate and O2 transmission rate are measured by the MOCON method (JIS K 7129(B)). In this embodiment, the water vapor transmission rate (WVTR) is measured at a water vapor transmission rate of 30 (g / m2) in an atmosphere at a temperature of 40°C and a humidity of 90%RH. 2 ·day) or less, preferably 25 (g / m 2 ·day) or less, more preferably 10 (g / m 2 ·day) or less, more preferably 3 (g / m 2 ·day) or less, more preferably 1 (g / m 2 ·day) or less, and even more preferably 0.1 (g / m 2 ·day) or less, and even more preferably 0.01 (g / m 2·day) or less, and even more preferably 0.001 (g / m 2 10 days or less, and even more preferably -4 (g / m 2 ·day) or less, most preferably 10 -5 (g / m 2 ·day) or less. The lower limit of the water vapor permeability is not limited, but for example, 10 -6 (g / m 2 The O2 permeability is 20 (cc / m 2) in an atmosphere with a temperature of 20°C and a humidity of 65%. 2 ·day·atm) or less, and 15 (cc / m 2 ·day·atm) or less is more preferable, and 10 (cc / m 2 ·day·atm) or less is more preferable, and 5 (cc / m 2 ·day·atm) or less, and more preferably 1 (cc / m 2 ·day·atm) or less, and more preferably 0.08 (cc / m 2 ·day·atm) or less, and more preferably 0.06 (cc / m 2 It is most preferable that the temperature is below 100°C (100°F / day·atm). In this embodiment, it is necessary for the barrier layer 11 to satisfy at least the water vapor permeability and the O 2 permeability, and it is preferable for the barrier layer 11 to satisfy both of them.

[0032] The barrier layer 11 is formed of a single layer or multilayer of inorganic films, a single layer or multilayer of organic films, or a multilayer of inorganic and organic films. While not limited to specific materials, the inorganic film can be one or more selected from SiO, SiO2, Al2O3, CaF2, SnO2, CeF3, MgO, MgAl2O4, SiNx, SiCN, SiC, SiOC, SiOAl, etc. Selecting SiO2, Al2O3, and MgAl2O4 from these materials effectively improves gas barrier properties. The organic film can be one or more selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polychlorotrifluoroethylene (PCTFE), etc. For example, when the barrier layer 11 includes an inorganic film, a substrate is required for forming the inorganic film; that is, a barrier film is formed by the substrate / barrier layer 11. This substrate can be the first substrate 3 in FIG. 1, and the barrier film can be formed by the first substrate 3 / barrier layer 11. In such a barrier film, the above-mentioned water vapor permeability and O2 permeability values ​​need to be satisfied by the barrier film as a whole, not by the barrier layer 11 alone. For example, the first substrate 3 as the substrate is a polycarbonate film with a thickness of 100 μm.

[0033] By providing an inorganic film on the barrier layer 11, excellent gas barrier properties can be obtained even if the barrier layer 11 is thin. Furthermore, by providing an organic film on the barrier layer 11, the barrier layer 11 can be easily handled. Therefore, by forming the barrier layer 11 into a laminated structure of an organic film and an inorganic film, both of the above-mentioned effects can be obtained. Furthermore, by forming the barrier layer 11 into a laminated structure of an organic film and an inorganic film, for example, when the electrochromic film 2 is bent into a curved shape, defects are less likely to occur in the organic film even if defects occur in the inorganic film, and gas barrier properties can be maintained.

[0034] The thickness of the barrier layer 11 is not limited, but is, for example, about 10 nm to 200 μm, preferably about 15 nm to 150 μm, and more preferably about 20 nm to 100 μm. Of these, the thickness of the inorganic film constituting the barrier layer 11 is preferably about 10 nm to 200 nm, more preferably about 15 nm to 150 nm, and even more preferably about 20 nm to 100 nm. An example of the inorganic film is a SiO2 film. The barrier layer 11 (barrier film) formed by depositing an inorganic film on the surface of an organic film substrate has a substrate thickness of about several tens of μm to several hundred μm, and the inorganic film can be thinned to the nanometer range as described above. In this embodiment, for example, the thickness of an inorganic film on the surface of a PET substrate or a barrier film formed by laminating an inorganic film and an organic film on the surface of a PET substrate is adjusted. In this embodiment, even if the thickness of the barrier layer 11 is thinned to several tens of μm, the water vapor permeability and O2 permeability within the above-mentioned numerical ranges can be obtained.

[0035] The barrier layer 11 has transparency as well as gas barrier properties. "Transparency" means transparency in the visible range and can be defined by visible range absorbance. For example, the visible range absorbance is preferably 0.1 Abs or less, and more preferably 0.09 Abs or less, at a wavelength of 400 to 750 mm, as measured using a UV-Visible-Near-Infrared Spectrophotometer UH4150 manufactured by Hitachi High-Tech Science Corporation.

[0036] Furthermore, the "transparency" of the barrier layer 11 means that light is not scattered, and can be defined by haze. The haze can generally be calculated by measuring the total light transmittance and diffuse transmittance of the barrier layer 11 using an integrating sphere light transmittance measuring device and using the following formula: Haze value (%) = Diffuse transmittance (%) / Total light transmittance (%) x 100 Here, the diffuse transmittance is a value obtained by subtracting the parallel light transmittance from the total light transmittance. In this embodiment, the haze value is set to 30% or less, preferably 20% or less, more preferably 10% or less, and even more preferably 1% or less. The transparency of the barrier layer 11 preferably satisfies both the above-mentioned visible light absorbance and haze. In the case of a resin film / inorganic film barrier film, the transparency is defined by the visible light absorbance and haze value of the barrier film.

[0037] Furthermore, reducing the difference in refractive index between the barrier layer 11 and the adjacent layer is preferable because it can reduce interference fringes. For example, in FIG. 1, the barrier layer 11 is disposed between the first substrate 3 and the hard coat layer 12, so the refractive index of the barrier layer 11 is preferably a value between the refractive index of the first substrate 3 and the refractive index of the hard coat layer 12. This reduces the refractive index difference between the barrier layer 11 and the adjacent layer. Specifically, the refractive index difference between the barrier layer 11 and the adjacent layer is adjusted to 0.4 or less, preferably 0.2 or less, and more preferably 0.1 or less.

[0038] When the barrier layer 11 also serves as the anti-reflection layer 13, it is preferable to optically design the barrier layer 11 so that reflected light is weakened relative to incident light.

[0039] Furthermore, the barrier layer 11 is preferably flexible. As will be described later, in a configuration in which the electrochromic film 2 of the present embodiment is bent into a curved shape, the flexibility of the barrier layer 11 allows the barrier layer 11 to deform appropriately to follow the shape of the electrochromic film 2. As described above, by forming the barrier layer 11 as a barrier film having a laminated structure of an inorganic film and an organic film, even if defects occur in the inorganic film when the barrier layer 11 is deformed, defects can be prevented from occurring in the organic film, and appropriate gas barrier properties can be maintained. Flexibility is evaluated by bending both sides of the barrier layer 11 toward each other and measuring the bending angle at which defects occur in the barrier layer 11. The bending angle is defined as the bending angle of each end from the flat position (0 degrees). The bending angle of each end is preferably 15 degrees or more, more preferably 30 degrees or more, and even more preferably 45 degrees or more. For example, when applied to eyeglass lenses, flexibility can be evaluated by the radius of curvature, and specifically, the radius of curvature is preferably 150 mm or less, more preferably 100 mm or less, even more preferably 90 mm or less, and even more preferably 60 mm or less.

[0040] In the first embodiment shown in Fig. 1, a barrier layer 11 is interposed between the electrochromic film 2 and the functional layer 15. This makes it possible to improve the gas barrier properties while maintaining the effects of the functional layer 15 (anti-reflection effect and water-repellent effect), effectively preventing the penetration of moisture and oxygen into the electrochromic layer 7, and achieving good responsiveness.

[0041] 1, the barrier layer 11 is provided separately from the functional layer 15, but the barrier layer 11 itself may have the functions of the hard coat layer 12 and the antireflection layer 13. This eliminates the need to form the hard coat layer 12 and the antireflection layer 13 in addition to the barrier layer 11, and simplifies the layered structure of the electrochromic element 10.

[0042] <Electrochromic element 20 according to the second embodiment> FIG. 2 is a schematic cross-sectional view of an electrochromic device 20 according to a second embodiment of the present invention.

[0043] The electrochromic element 20 of the second embodiment shown in Figure 2 has the same configuration as the electrochromic element 10 of the first embodiment shown in Figure 1, but further includes a barrier layer 21 disposed between the support 1 and the electrochromic film 2.

[0044] The support 1 is preferably a resin substrate such as polycarbonate resin from the viewpoint of formability and manufacturing costs, but has a higher water absorption rate than a glass substrate. For this reason, in the second embodiment, a barrier layer 21 is also provided on the support 1 side, thereby preventing the penetration of moisture and oxygen from the support 1 side. In FIG. 2, the support 1 and the barrier layer 21 are bonded together via an adhesive layer 22, but if the support 1 and the barrier layer 21 can be bonded together directly, the adhesive layer 22 is not essential.

[0045] 2, an electrochromic element 20 according to a second embodiment is provided with two barrier layers 11 and 21 sandwiching the electrochromic layer 7, and can effectively prevent moisture and oxygen from penetrating from both the functional layer 15 side and the support 1 side as viewed from the electrochromic layer 7. This makes it possible to more effectively improve gas barrier properties and obtain better responsiveness. In the second embodiment shown in FIG. 2, a barrier film can also be formed by depositing a barrier layer 21 on the surface of the second substrate 4.

[0046] <Electrochromic element 30 according to the third embodiment> FIG. 3 is a schematic cross-sectional view of an electrochromic device 30 according to a third embodiment of the present invention.

[0047] In Figure 3, barrier layers 31 and 32 are arranged between the first electrode layer 5 located on the inner surface of the first substrate 3 and the first substrate 3, and between the second electrode layer 6 located on the inner surface of the second substrate 4 and the second substrate 4, respectively, which constitute the electrochromic film 2.

[0048] The first substrate 3 and the second substrate 4 are, for example, resin films such as polycarbonate, and in order to improve the gas barrier properties, it is preferable to provide barrier layers 31, 32 on the inner surfaces of the substrates 3, 4. For example, the barrier layers 31, 32 are inorganic films such as SiO2, and a barrier film can be formed by depositing the barrier layers 31, 32 on the inner surfaces of the first substrate 3 and the second substrate 4. This makes the barrier film easy to handle and can prevent moisture and oxygen from penetrating the electrochromic layer 7, effectively improving the gas barrier properties and achieving good responsiveness.

[0049] Since the stack of the first electrode layer 5 / electrochromic layer 7 / second electrode layer 6 is preferably a continuous structure, it is preferable that the barrier layer be provided on the outside of this stack structure, as shown in Figure 3.

[0050] <Other forms> In this embodiment, the barrier layer may be disposed anywhere in the laminate structure constituting the electrochromic element; the arrangement of the barrier layer is not limited to those shown in FIGS. 1 to 3, and the number of barrier layers is not limited. The barrier layer may be disposed inside the laminate structure or on the surface (outer surface) of the laminate structure. However, it is preferable to dispose the barrier layer in a position that does not impair the electrochromic phenomenon or other functions, and also in an appropriate position taking into consideration the manufacturing process. For this reason, as described above, it is preferable that the electrochromic layer 7 and each electrode layer 5, 6 are in direct contact with each other, and therefore the barrier layer is preferably disposed at least on the outside of the electrode layers 5, 6. In addition, it is more preferable to dispose a barrier layer in the laminated structure that constitutes the electrochromic element and to provide the seal layer 16 with gas barrier properties.

[0051] For example, the sealing layer 16 is preferably formed from a material that has gas barrier properties and allows patterning. For example, at least one of UV-curable resin, thermosetting resin, low-melting-point alloy, and low-melting-point glass can be selected. UV-curable resin is preferable because it can be cured without high-temperature heating.

[0052] <Application> Although the application of the electrochromic element of this embodiment is not limited thereto, it can be preferably applied to photochromic eyeglass lenses. In eyeglass lenses, the support 1 is a lens substrate. The electrochromic element of this embodiment may be applied to devices other than eyeglass lenses, such as electrochromic light control devices and anti-glare mirrors.

[0053] <Method for manufacturing electrochromic element according to the present embodiment> FIG. 4 is an explanatory diagram showing a method for manufacturing an electrochromic element according to the present embodiment.

[0054] In Fig. 4(a), an electrochromic film 2 is prepared, which has a pair of substrates 3, 4, electrode layers 5, 6 disposed inside each of the substrates 3, 4, and an electrochromic layer 7 sandwiched between the electrode layers 5, 6. Note that the layered structure of the electrochromic film 2 is not limited to this, and may be a layered structure other than that shown in Fig. 4(a).

[0055] Next, the electrochromic film 2 is set in a mold (not shown), and the material constituting the support 1 is injected into the mold to form the support 1. However, as shown in FIG. 4(b), the electrochromic film 2 may be preformed into a curved surface. That is, when the electrochromic element of this embodiment is applied to an eyeglass lens, since the eyeglass lens has a three-dimensional curved surface, it is preferable to preform the electrochromic film 2 into a three-dimensional curved surface before molding the support 1. For example, the electrochromic film 2 is set in a mold while being heated, and is pressed into a spherical shape.

[0056] A barrier layer formation step (1) can be performed between FIGS. 4(a) and 4(b). That is, a barrier layer can be formed on the surface (outer surface) of the flat electrochromic film 2 shown in FIG. 4(a). For example, a barrier layer 11 can be formed on the surface of the first substrate 3 of the electrochromic film 2 (see FIG. 1). Alternatively, barrier layers 11 and 21 can be formed on the surfaces of the substrates 3 and 4 (see FIG. 2). Alternatively, the barrier layer 21 can be formed only on the surface of the second substrate 4. The barrier layers 11 and 21 can be formed by dry film formation methods such as CVD, sputtering, and vapor deposition, or wet film formation methods such as coating and printing. Alternatively, the barrier layers 11 and 21 can be formed directly on the surfaces of the substrates 3 and 4 to form a barrier film. Alternatively, a separate barrier film can be prepared and attached to the substrates 3 and 4 via an adhesive layer. Alternatively, the barrier film can be attached directly to the surfaces of the substrates 3 and 4 by thermocompression bonding or the like without an adhesive layer.

[0057] Next, in FIG. 4(c), the support 1 is molded to obtain an electrochromic device intermediate 42 in which the electrochromic film 2 is formed on the surface of the support 1. In this embodiment, a barrier layer forming step (2) can be provided between FIG. 4(b) and FIG. 4(c).

[0058] In the barrier layer forming step (1), the electrochromic film 2 is subsequently preformed into a curved shape, so the barrier layers 11, 21 provided on the surface of the electrochromic film 2 must be flexible. On the other hand, in the barrier layer forming step (2), after the electrochromic film 2 is preformed into a curved shape, the barrier layers 11, 21 can be formed along the curved surface by a dry film forming method or a wet film forming method.

[0059] 4(c), a functional layer 15 consisting of a hard coat layer 12, an anti-reflection layer 13, and a water-repellent layer 14 is formed on the surface of the electrochromic film 2. At this time, in the barrier layer formation step (3), the hard coat layer 12 and the anti-reflection layer 13 can also be formed from a material having gas barrier properties. Thereafter, in FIG. 4(d), the electrochromic element intermediate 42 is cut into a predetermined shape to obtain the electrochromic element 10.

[0060] 4 may be performed at least once, or may be performed multiple times. Alternatively, the barrier layer may be formed at a timing other than the barrier layer forming steps (1) to (3).

[0061] To form the electrochromic element 30 shown in FIG. 3, it is necessary to dispose the barrier layers 31 and 32 in the step of forming the electrochromic film 2 shown in FIG. 4(a).

[0062] In this embodiment, the barrier layer forming steps (1) to (3) can be included in the process for manufacturing an electrochromic element, and an electrochromic element with excellent gas barrier properties can be manufactured without complicating the manufacturing process. [Example]

[0063] Hereinafter, this embodiment will be described more specifically using examples and comparative examples.

[0064] <Experiments on water vapor permeability, O2 permeability, visible light absorbance, and haze> In the experiment, a barrier film consisting of a substrate and a barrier layer was used. The substrate was a 100 μm thick polycarbonate film, and a SiO2 film was deposited as a barrier layer on the surface of the polycarbonate film by CVD (Chemical Vapor Deposition).

[0065] The thickness of the SiO2 film was changed to 0 nm, 5 nm, 20 nm, 50 nm, 100 nm, and 2100 nm, and the water vapor permeability, O2 permeability, visible light absorbance, and haze were determined for each experiment. Water vapor transmission rate and O2 transmission rate were measured by the Mocon method (JIS K 7129(B)). Water vapor transmission rate (WVTR) was measured in an atmosphere with a temperature of 40°C and a humidity of 90%RH. O2 transmission rate was measured in an atmosphere with a temperature of 20°C and a humidity of 65%RH.

[0066] The visible region absorbance was measured using an ultraviolet-visible-near-infrared spectrophotometer UH4150 manufactured by Hitachi High-Tech Science Corporation at a wavelength of 400 to 750 mm.

[0067] The haze was determined by measuring the total light transmittance and diffuse transmittance of the barrier film using an integrating sphere light transmittance measuring device, and calculating the haze value (%) = diffuse transmittance (%) / total light transmittance (%) × 100. The experimental results are shown in Table 1 below.

[0068] [Table 1]

[0069] <Visual inspection> Furthermore, the electrochromic element 10 shown in FIG. 1 was produced using each of the barrier films of Experimental Examples 1 to 6. As an accelerated test, each experimental sample was left in a thermo-hygrostat at a temperature of 40°C and a humidity of 90% for 240 hours, and then subjected to 10 current tests (which repeatedly caused coloring and fading) before being visually inspected.

[0070] In Experimental Examples 1 to 3, the electrochromic elements were in the same state before and after the constant temperature and humidity test, and no deterioration was observed during coloring, indicating that they maintained good condition.

[0071] On the other hand, in Experimental Example 4, a visual inspection of the electrochromic lens after leaving it in a thermo-hygrostat revealed that the electrochromic lens had yellowed. In addition, the color density of the electrochromic lens became lighter and it also became cloudy.

[0072] In addition, in Experimental Example 5, a visual inspection of the electrochromic lens after leaving it in a thermo-hygrostat revealed that the electrochromic lens had yellowed. In addition, the color density of the electrochromic lens after coloring became lighter.

[0073] In Experimental Examples 4 and 5, it is believed that moisture penetrated into the interior of the electrochromic lens, causing deterioration in the state of the electrochromic element after the constant temperature and humidity test.

[0074] In Experimental Example 6, fine cracks were found in the SiO2 film after it was formed. The electrochromic element was disassembled and its haze was measured, which was 30%. In Experimental Example 6, it was found that the barrier layer was cracked, causing a significant deterioration in haze and O2 transmittance. It is believed that the cracks in the barrier layer were caused by stress in the SiO2 film, which was too thick. From the experimental results, Experimental Examples 1 to 3 were designated as Examples, and Experimental Examples 4 to 6 were designated as Comparative Examples. [Industrial Applicability]

[0075] The electrochromic element of the present invention has excellent gas barrier properties, and therefore, when the electrochromic element is used as a lens for photochromic glasses, for example, it becomes possible to obtain a feeling of use with excellent response.

[0076] This application is based on Japanese Patent Application No. 2021-082860, filed on May 17, 2021, the entire contents of which are incorporated herein by reference.

Claims

1. An electrochromic element including a support and an electrochromic film having a pair of electrode layers and an electrochromic layer provided between the pair of electrode layers, the electrochromic element comprising: a barrier layer is laminated on the laminate structure constituting the electrochromic element, The electrochromic film includes a pair of substrates, a pair of electrode layers laminated between the pair of substrates, and the electrochromic layer, a sealing layer is provided between the pair of substrates and around the electrochromic layer; the barrier layers are disposed between the pair of substrates and the pair of electrode layers, respectively, and extend to face the sealing layer so as to be in contact with the sealing layer; The sealing layer also has gas barrier properties. An electrochromic element characterized by:

2. 2. The electrochromic device according to claim 1, wherein the barrier layer has gas barrier properties and transparency.

3. 3. The electrochromic device according to claim 1, wherein the barrier layer is further disposed between the support and the electrochromic film.

4. 3. The electrochromic element according to claim 1, wherein the support is a lens substrate.

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