Electrochromic sheet and electrochromic device

Abstract

To provide an electrochromic sheet with which it is possible to improve freedom of design.SOLUTION: An electrochromic sheet 100 comprises: a first transparent base material 1 (support layer); an electrolyte layer 4 provided on the first transparent base material 1 (support layer); an electrochromic layer 3 provided on at least one side of the electrolyte layer 4; and a pair of transparent electrode layers (first transparent electrode layer 2, second transparent electrode layer 6) located on top of the first transparent base material layer 1 (support layer) so as to sandwich the electrolyte layer 4 and the electrochromic layer 3, the electrochromic sheet 100 being constituted to satisfy condition 1 below. (Condition 1) When reflected light obtained by irradiating the face of the electrochromic sheet 100 on the side of the first transparent base material layer 1 (support layer) with light from a D65 light source at an incident angle 90° is measured at a view angle 10° using a spectral photometer, a* and b* in CIE1976 L*a*b* chromaticity coordinates of the reflected light are -15 to 15, and -20 to 10, respectively.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an electrochromic sheet and an electrochromic device. [Background technology]

[0002] Electrochromic elements are known as elements that utilize electrochromism, a phenomenon in which a reversible redox reaction occurs when a voltage is applied, causing a reversible change in transmittance. For example, a color can be produced by applying a positive voltage to an electrochromic element, and the color can be removed by applying a negative voltage to make the element transparent. Therefore, by providing a switch that can switch between applying a positive voltage and a negative voltage, the electrochromic element can be made to color and remove color at any time.

[0003] Also, in order to improve the usability of the electrochromic element, a structure in which the electrochromic element is sandwiched between a pair of transparent electrode layers for positive and negative electrodes is widely known. In order to obtain good light transmittance, the material of such transparent electrode layers is usually ITO (Indium Tin Oxide), which is indium oxide doped with tin oxide.

[0004] For example, Patent Document 1 (JP 2022-176332 A) discloses an electronic element for electronic dimming glasses, which has a pair of transparent electrode layers using ITO and a dimming layer provided between the pair of transparent electrode layers. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2022-176332 A Summary of the Invention [Problem to be solved by the invention]

[0006] Conventionally, electrochromic elements such as that disclosed in Patent Document 1 have been used in lenses for eyewear and the like, and therefore, attention has been focused on light transmittance in order to transmit light well. Meanwhile, with the recent increase in interest in electrochromic elements and the rise in the level of technology, there is a demand for lenses for eyewear and the like that utilize electrochromic elements to be able to be designed with a desired color with high precision.

[0007] The present inventors have conducted extensive research with a view to increasing the freedom of color design and have found that, even if the conventional technology disclosed in Patent Document 1 has good light transmittance, there is room for improvement in terms of the freedom of color design due to the slightly yellowish reflected light. The inventors then devised a new index for controlling such reflected light and discovered that the above problem could be solved by designing an electrochromic sheet to satisfy this index, thereby completing the present invention. [Means for solving the problem]

[0008] The inventors conducted intensive research to improve the freedom of color design, and as a result, devised a new index for controlling the slightly yellowish reflected light, discovered that it is effective to design an electrochromic sheet to satisfy this index, and thus completed the present invention.

[0009] According to the present invention, the following electrochromic sheet and related techniques are provided.

[0010] [1] A support layer; an electrolyte layer provided on the support layer; an electrochromic layer provided on at least one surface of the electrolyte layer; a pair of transparent electrode layers disposed on the support layer so as to sandwich the electrolyte layer and the electrochemical layer; The electrochromic sheet is configured to satisfy the following condition 1. (Condition 1) The surface of the electrochromic sheet facing the support layer is irradiated with light from a D65 light source at an incident angle of 90°, and the reflected light is measured using a spectrophotometer at a viewing angle of 10°. The CIE1976L * a * b * Chromaticity coordinates a * is -15 to 15, b * is between -20 and 10. [2] The electrochromic sheet according to [1], An electrochromic sheet further configured to satisfy the following condition 2. (Condition 2) The surface of the electrochromic sheet facing the support layer is irradiated with light from a D65 light source at an incident angle of 90°, and the reflected light is measured using a spectrophotometer at a viewing angle of 10°. The CIE1976L * a * b * L in chromaticity coordinates * is between 20 and 50. [3] The electrochromic sheet according to [1] or [2], An electrochromic sheet further configured to satisfy the following condition 3. (Condition 3) The electrochromic sheet has a surface on the support layer side with light from a D65 light source irradiated at an incident angle of 90°, and the transmitted light is measured at a viewing angle of 10° using a spectrophotometer, resulting in a transmittance of 70 to 99%. [4] An electrochromic sheet according to any one of [1] to [3], a sealing material on the support layer that covers the side surfaces of the electrolyte layer and the electrochemical layer; An electrochromic sheet further configured to satisfy the following condition 4. (Condition 4) Using the electrochromic sheet, a test piece (maximum length 20 mm or more) is prepared with the electrolyte layer as the center and the sealing material as the outer edge, both ends of the test piece are chucked with chucking parts, the center of the test piece is pressed with 30 N for 30 seconds, and the difference in depth between the center of the test piece before pressing and the center of the test piece after pressing is the deformation amount (mm). The deformation amount is 0.01 mm to 0.09 mm. [5] An electrochromic sheet according to any one of [1] to [4], The electrochromic sheet, wherein the transparent electrode layer has a thickness of 40 to 200 nm. [6] An electrochromic sheet according to any one of [1] to [5], An electrochromic sheet, wherein at least one of the pair of transparent electrode layers has a multi-layer structure. [7] An electrochromic sheet according to any one of [1] to [6], The electrochromic sheet, wherein the transparent electrode layer contains one or more materials selected from the group consisting of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), zinc-doped indium oxide (IZO), silver (Ag) and silver alloys, as well as polypyrrole, polyaniline, polythiophene, poly(p-phenylene), polyfluorene and derivatives thereof. [8] An electrochromic sheet according to any one of [1] to [6], The electrochromic sheet has a single-layer or multi-layer structure, and the transparent electrode layer is made of any material selected from the group consisting of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), zinc-doped indium oxide (IZO), silver (Ag), silver alloys, and polypyrrole, polyaniline, polythiophene, poly(p-phenylene), polyfluorene, and derivatives thereof. [9] An electrochromic sheet according to any one of [1] to [8], An electrochromic sheet, wherein the pair of transparent electrode layers are made of different materials.

[10] An electrochromic sheet according to any one of [1] to [8], An electrochromic sheet, wherein the pair of transparent electrode layers are made of the same material.

[11] An electrochromic sheet according to any one of [1] to

[10] , The support layer is an electrochromic sheet containing one or more resins selected from episulfide-based resins, thiourethane-based resins, acrylic-based resins, polycarbonate-based resins, urethane-based resins, polyamide-based resins, polyester-based resins, cellulose-based resins, cycloolefin polymers (COP), cycloolefin copolymers (COC), norbornene-based resins, and silicone-based resins.

[12] An electrochromic device using the electrochromic sheet described in any one of [1] to

[11] . Effect of the Invention

[0011] The present invention provides an electrochromic sheet that can improve the freedom of color design. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an electrochromic sheet according to an embodiment of the present invention. [Diagram 2] 1A to 1C are schematic diagrams showing a method for manufacturing a lens using the electrochromic sheet of the present embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. In order to avoid complexity, when there are multiple identical components in the same drawing, only one of them may be marked with a symbol, and not all of them may be marked with a symbol. All drawings are for illustrative purposes only. The shape and dimensional ratio of each component in the drawings do not necessarily correspond to the actual product.

[0014] In this specification, the expression "a to b" in the description of a numerical range means a or more and b or less, unless otherwise specified. For example, "1 to 5 mass%" means "1 mass% or more and 5 mass% or less." In addition, the lower limit and upper limit of a numerical range can be arbitrarily combined with the lower limit and upper limit of another numerical range.

[0015] Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more kinds.

[0016] In this embodiment, "covering" is not limited to being continuous, but may include some discontinuous portions.

[0017] <Electrochromic sheet> FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of an electrochromic sheet 100. As shown in FIG. As shown in FIG. 1, the electrochromic sheet 100 comprises a laminate (hereinafter also referred to as "electrochromic element 10") in which an electrolyte layer 4, a first electrochromic layer 3, and a second electrochromic layer 5 are laminated in order, a sealing material 8 covering the side surfaces of the electrochromic element 10, and a pair of support layers (a first transparent substrate layer 1 and a second transparent substrate layer 7) sandwiching the top and bottom surfaces of the electrochromic element 10 and the sealing material 8 therebetween. In other words, the electrochromic sheet 100 comprises a first electrochromic layer 3, an electrolyte layer 4, a second electrochromic layer 5, and a second transparent substrate layer 7, which are sequentially stacked on a first transparent substrate layer 1, and the sides of the first electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 are each covered with a sealing material 8.

[0018] Furthermore, the electrochromic sheet 100 of this embodiment has a first transparent electrode layer 2 between the first transparent substrate layer 1 and the first electrochromic layer 3, and has a second transparent electrode layer 6 between the second transparent substrate layer 7 and the second electrochromic layer 5. In other words, the electrochromic sheet 100 includes a pair of electrode layers (first transparent electrode layer 2 and second transparent electrode layer 6) located on a first transparent substrate layer 1 (support layer) so as to sandwich an electrochromic layer 3, an electrolyte layer, and an electrochromic layer 5. In this embodiment, the first transparent electrode layer 2 and the second transparent electrode layer 6 are transparent. The term "transparent" means that the transmittance of transmitted light obtained by irradiating light from a D65 light source at an incident angle of 90° is 65% or more and the haze is 3.0 or less.

[0019] 1, the electrochromic sheet 100 has a first columnar conductive portion 22 and a second columnar conductive portion 62 penetrating through the sealing material 8 in the thickness direction. The first columnar conductive portion 22 and the second columnar conductive portion 62 are both electrically connected to the electrolyte layer 4. Moreover, the first columnar conductive portion 22 penetrates the sealing material 8, and reaches from the first auxiliary electrode layer 21 provided on the first transparent electrode layer 2 to the second transparent substrate layer 7. Similarly, the second columnar conductive portion 62 penetrates the sealing material 8, and reaches from the second auxiliary electrode layer 61 provided on the second transparent electrode layer 6 to the first transparent substrate layer 1.

[0020] In this embodiment, the electrochromic sheet 100 will be described taking as an example a case in which the first electrochromic layer 3 and the second electrochromic layer 5 are laminated on both sides of the electrolyte layer 4, but only one of the electrochromic layers may be provided.

[0021] Furthermore, while FIG. 1 shows a portion of an electrochromic sheet 100 that focuses on a single electrochromic element 10 and the sealing material 9 that surrounds it, the electrochromic sheet 100 may also be one in which multiple electrochromic elements 10 are partitioned by sealing material 8 that covers the sides of each electrochromic element 10.

[0022] The electrochromic sheet 100 of this embodiment is configured to satisfy the following condition 1. This improves the degree of freedom in designing the color of the electrochromic sheet 100 and lenses and the like using the same. That is, in the conventional technology, it was sometimes impossible to obtain a desired color even when the electrochromic sheet was colored, whereas with the electrochromic sheet 100 of this embodiment, the a of the reflected light measured by a predetermined method can be obtained. * value and b * By controlling the value, it is possible to prevent the reflected light itself from having a color tone, making it easier to obtain a desired color tone. Furthermore, the electrochromic sheet 100 of this embodiment can provide good processability (mechanical strength).

[0023] (Condition 1) The surface of the electrochromic sheet 100 on the side of the first transparent substrate layer 1 (support layer) is irradiated with light from a D65 light source at an incident angle of 90°, and the reflected light is measured using a spectrophotometer at a viewing angle of 10°. The CIE1976L * a * b * Chromaticity coordinates a * is -15 to 15, b * is between -20 and 10.

[0024] Although the details of the mechanism by which such an effect is obtained are not clear, it is thought that the a * value and b * It is believed that by controlling these values, the apparent color of the electrochromic sheet 100 can be highly controlled, allowing a desired color to be obtained and expanding the freedom of design.

[0025] In condition 1, a * is −15 to 15, preferably −10 to 10, and more preferably −5 to 5. In condition 1, b * is in the range of -20 to 10, preferably in the range of -15 to 5, and more preferably in the range of -10 to 0.

[0026] The electrochromic sheet 100 of the present embodiment is further configured to satisfy the following condition 2. This makes it possible to improve the degree of freedom in designing the color of the electrochromic sheet 100 and lenses and the like using the same with a higher degree of precision.

[0027] (Condition 2) The surface of the first transparent substrate layer 1 (support layer) of the electrochromic sheet 100 is irradiated with light from a D65 light source at an incident angle of 90°, and the reflected light is measured using a spectrophotometer at a viewing angle of 10°. The CIE1976L * a * b * L in chromaticity coordinates * is between 20 and 50.

[0028] In condition 2, L * is 20 to 50, preferably 25 to 45, and more preferably 30 to 40.

[0029] The electrochromic sheet 100 of the present embodiment is further configured to satisfy the following condition 3. This makes it possible to improve the degree of freedom in designing the color of the electrochromic sheet 100 and lenses and the like using the same with a higher degree of precision.

[0030] (Condition 3) When the surface of the electrochromic sheet 100 on the side of the first transparent substrate layer 1 (support layer) is irradiated with light from a D65 light source at an incident angle of 90° and the transmitted light is measured using a spectrophotometer at a viewing angle of 10°, the transmittance is 70 to 99%.

[0031] In condition 3, the transmittance is 70 to 99%, preferably 75 to 99%, and more preferably 80 to 99%.

[0032] Furthermore, when the surface of the electrochromic sheet 100 on the side of the first transparent substrate layer 1 (support layer) is irradiated with light from a D65 light source at an incident angle of 90° and the reflected light obtained is measured using a spectrophotometer at a viewing angle of 10°, the reflectance is preferably 5 to 15%, and more preferably 8 to 12%.

[0033] In this embodiment, since the electrochromic sheet 100 has the first electrochromic layer 3 and the second electrochromic layer 5 laminated on both sides of the electrolyte layer 4, in conditions 1 to 3, the surface on the second transparent substrate layer (support layer) side may be irradiated with light from a D65 light source at an incident angle of 90° to measure the reflected light.

[0034] The electrochromic sheet 100 of the present embodiment is further configured to satisfy the following condition 4. This makes it possible to improve the degree of freedom in designing the color of the electrochromic sheet 100 and lenses and the like using the same with a higher degree of precision.

[0035] (Condition 4) A test piece (maximum length 20 mm or more) is prepared using the electrochromic sheet 100, with the electrolyte layer 4 as the center and the sealing material 8 as the outer edge, both ends of the test piece are chucked with chucking parts, the center of the test piece is pressed with 30 N for 30 seconds, and the difference in depth between the center of the test piece before pressing and the center of the test piece after pressing is the deformation amount (mm). The deformation amount is 0.01 mm to 0.09 mm.

[0036] In condition 4, the deformation amount is 0.01 mm to 0.09 mm, preferably 0.02 to 0.08 mm, and more preferably 0.03 to 0.07 mm.

[0037] This improves mechanical strength while maintaining good processability. More specifically, even when a load is applied to the electrolyte layer 4, for example, during punching or deformation of the electrochromic sheet 100 into a curved shape, during surface processing for making a prescription lens, or during chucking during lens cutting, deformation or denting of the electrolyte layer 4 can be suppressed.

[0038] Furthermore, it is preferable that the electrochromic sheet 100 does not have a yield point when measured under condition 4. This allows for more stable and favorable processability to be obtained.

[0039] In the above condition 4, the shape of the test piece is appropriately adjusted according to the shape of the electrolyte layer 4 and the sealing portion 8 covering the side surface of the electrolyte layer 4, but the maximum length is at least 20 mm or more. When the shape of the test piece is a rectangle, it is preferable that one side is 20 mm or more and the other side is 30 mm or more. The upper limit of the shape of the test piece is not particularly limited, and it is sufficient that it does not protrude from the stage of the measuring device. The central portion is a region including the center point of the test piece in a plan view.

[0040] In this embodiment, the electrochromic sheet 100 that satisfies the above conditions 1 to 4 can be appropriately prepared by a person skilled in the art by combining known methods. For example, this can be achieved by adjusting the constituent materials, layer configuration, and thickness of the first transparent electrode layer 2 and the second transparent electrode layer 6, the combination of the first transparent electrode layer 2 and the second transparent electrode layer 6, the selection of the material of the sealing material 9, the material and preparation procedure of the electrolyte layer 4, the manufacturing procedure and manufacturing conditions of the electrochromic sheet 100, etc. Specifically, examples include using a material other than ITO as the constituent material of the first transparent electrode layer 2 and the second transparent electrode layer 6, and forming a multi-layer structure.

[0041] Hereinafter, each component of the electrochromic sheet 100 will be described in detail.

[0042] [Transparent electrode layer] In this embodiment, the first transparent electrode layer 2 and the second transparent electrode layer 6 are a pair of electrode layers that sandwich the first electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 therebetween.

[0043] The first transparent electrode layer 2 and the second transparent electrode layer 6 are electrodes that supply electrons between the first transparent electrode layer 2 and the second transparent electrode layer 6, or receive electrons from between the first transparent electrode layer 2 and the second transparent electrode layer 6, when a positive voltage or a negative voltage is applied to the first electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5, respectively. The first transparent electrode layer 2 is provided on the surface of the first electrochromic layer 3 opposite to the electrolyte layer 4. The second transparent electrode layer 6 is provided on the surface of the second electrochromic layer 5 opposite to the electrolyte layer 4.

[0044] The first transparent electrode layer 2 and the second transparent electrode layer 6 may be either a single layer or a multilayer structure in which two or more layers are laminated, and it is preferable that at least one of them has a multilayer structure. Moreover, the layer structures of the first transparent electrode layer 2 and the second transparent electrode layer 6 may be the same as or different from each other, and may be symmetrical with respect to the electrolytic layer 4.

[0045] The average thicknesses of the first transparent electrode layer 2 and the second transparent electrode layer 6 are adjusted so as to obtain the electrical resistance value required for the oxidation-reduction reaction of the first electrochromic layer 3 and the second electrochromic layer 5, and to improve the freedom of design. The thickness of the first transparent electrode layer 2 and the second transparent electrode layer 6 is preferably 40 to 200 nm, more preferably 70 to 175 nm, and further preferably 100 to 150 nm. By setting the thickness of the first transparent electrode layer 2 and the second transparent electrode layer 6 to the above lower limit or more, it is possible to prevent the resistance value from increasing too much and maintain the performance as an electrochromic sheet. On the other hand, by setting the thickness of the first transparent electrode layer 2 and the second transparent electrode layer 6 to the above upper limit or less, it is possible to prevent the transmittance from decreasing too much and improve the freedom of design of the appearance. In addition, by setting the thickness of the first transparent electrode layer 2 and the second transparent electrode layer 6 within the range of the above lower limit or more and the above upper limit or less, it is possible to keep the color of the reflected light transparent and improve the freedom of design of the lens.

[0046] Furthermore, for example, when ITO is used as the constituent material of the first transparent electrode layer 2 and the second transparent electrode layer 6, each is independently set to preferably 50 nm or more and 200 nm or less, more preferably 100 nm or more and 150 nm or less.

[0047] Between each layer between the first transparent electrode layer 2 and the second transparent electrode layer 6, an intermediate layer such as an insulating porous layer or a protective layer may be provided.

[0048] The thicknesses of the first transparent electrode layer 2 and the second transparent electrode layer 6 may be the same or different from each other. In addition, the thicknesses of the first transparent electrode layer 2 and the second transparent electrode layer 6 are preferably set according to the constituent materials described below.

[0049] The constituent materials of the first transparent electrode layer 2 and the second transparent electrode layer 6 are not particularly limited as long as they are transparent conductive materials, and for example, one or more selected from tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), zinc-doped indium oxide (IZO), silver (Ag) and silver alloys, as well as polypyrrole, polyaniline, polythiophene, poly(p-phenylene), polyfluorene, and derivatives thereof can be used in combination.

[0050] The constituent materials of the first transparent electrode layer 2 and the second transparent electrode layer 6 may be the same or different from each other. In particular, from the viewpoint of improving the degree of freedom in design, when one of the first transparent electrode layer 2 and the second transparent electrode layer 6 contains tin-doped indium oxide (ITO), it is preferable that the other does not contain tin-doped indium oxide (ITO), and it is more preferable that both contain tin-doped indium oxide (ITO).

[0051] Specifically, the first transparent electrode layer 2 and the second transparent electrode layer 6 are preferably a single layer or multilayer structure having a layer made of any material selected from tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), zinc-doped indium oxide (IZO), silver (Ag), silver alloy, and polypyrrole, polyaniline, polythiophene, poly(p-phenylene), polyfluorene, and derivatives thereof. In particular, from the viewpoint of improving the degree of freedom of design, when one of the first transparent electrode layer 2 and the second transparent electrode layer 6 includes a layer made of tin-doped indium oxide (ITO), it is preferable that the other does not include a layer made of tin-doped indium oxide (ITO), it is more preferable that both are layers containing tin-doped indium oxide (ITO), and it is even more preferable that both are layers containing tin-doped indium oxide (ITO).

[0052] Examples of methods for producing the first transparent electrode layer 2 and the second transparent electrode layer 6 include vacuum deposition, sputtering, ion plating, etc. In addition, as long as the materials for the first transparent electrode layer 2 and the second transparent electrode layer 6 can be applied, various printing methods such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing can be used.

[0053] [Electrolyte layer] The electrolyte layer 4 is disposed between the first electrochromic layer 3 and the second electrochromic layer 5, and contains an electrolyte having ion conductivity.

[0054] The average thickness of the electrolyte layer 4 is not particularly limited, but is preferably set to about 20 μm or more and 100 μm or less, and more preferably about 40 μm or more and 80 μm or less.

[0055] The electrolyte layer 4 includes a binder resin and an electrolyte.

[0056] The binder resin is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable that the binder resin contains a urethane resin unit in terms of the phase separation temperature and film strength as a polymer membrane. Also, by containing a polyethylene oxide (PEO) chain, the compatibility with the electrolyte is improved and the phase separation temperature can be increased. Also, by containing a polymethyl methacrylate (PMMA) chain, the compatibility with the electrolyte is improved and the phase separation temperature can be increased, similarly to the case of containing a PEO chain.

[0057] The electrolyte is not particularly limited, but examples thereof include inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids, and alkali supporting salts. Specific examples include LiClO4, LiBF4, LiAsF6, LiPF6, LiCF3SO3, LiCF3COO, KCl, NaClO3, NaCl, NaBF4, NaSCN, KBF4, Mg(ClO4)2, Mg(BF4)2, etc., and one or a combination of two or more of these can be used.

[0058] In addition, ionic liquids can also be used as electrolyte materials. Among these ionic liquids, organic ionic liquids are preferably used because they have a molecular structure that shows liquidity over a wide temperature range including room temperature and are easy to handle.

[0059] As the molecular structure of the organic ionic liquid, the cationic component may be, for example, an imidazole derivative such as N,N-dimethylimidazole salt, N,N-methylethylimidazole salt, or N,N-methylpropylimidazole salt; a pyridinium derivative such as N,N-dimethylpyridinium salt or N,N-methylpropylpyridinium salt; or an aliphatic quaternary ammonium derivative such as trimethylpropylammonium salt, trimethylhexylammonium salt, or triethylhexylammonium salt. In addition, it is preferable to use a fluorine-containing compound as the anionic component, taking into consideration stability in the atmosphere, such as BF4 - , CF3SO3 - , PF4 - , (CF3SO2)2N - etc.

[0060] Such an electrolyte material is preferably an ionic liquid containing any combination of cationic and anionic components.

[0061] The ionic liquid may be directly dissolved in any of the photopolymerizable monomers, oligomers, and liquid crystal materials. If the ionic liquid has poor solubility in these materials, it may be dissolved in a small amount of solvent to obtain a solution, and then this solution may be mixed with any of the photopolymerizable monomers, oligomers, and liquid crystal materials to dissolve the ionic liquid.

[0062] Examples of the solvent include propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, polyethylene glycol, alcohols, and mixed solvents thereof.

[0063] The electrolyte filled as the electrolyte layer 4 may be either solid or liquid, but in addition to the electrolyte being a low-viscosity liquid, it may take various forms, such as a gel, a polymer cross-linked type, or a liquid crystal dispersion type. Of these, it is preferable that the electrolyte be formed into a gel or solid state. This can improve the element strength and reliability of the electrochromic element 10.

[0064] A preferred method for making the electrolyte layer 4 solid is, for example, a method in which a liquid containing an electrolyte and a solvent is held in a binder resin. This allows the electrolyte layer 4 to have both high ionic conductivity and solid strength. In addition, a photocurable resin is preferred as the polymer resin. This allows the electrolyte layer 4 to be solid at a lower temperature and in a shorter time than when the electrolyte layer 4 is solidified by thermal polymerization or evaporation of a solvent.

[0065] When the electrolyte layer 4 is in a gel state, it can be prepared, for example, as follows. First, a composition solution is prepared, and the prepared composition solution is sandwiched between a mold or a film and polymerized by a cast polymerization method or the like. The composition solution can be prepared by mixing an electrolyte solution obtained by mixing the ionic liquid or solid electrolyte with a solvent, a polymerizable material, a urethane acrylate monomer, and, if necessary, an acrylate monomer having a PEO chain, and, if necessary, an acrylate monomer having a PMMA chain in a desired ratio, and, if necessary, the polymerization initiator and other components can be mixed. As another preparation method, a method of applying a composition solution before polymerization onto one electrochromic layer and polymerizing it by ultraviolet irradiation or heating can be used. Also, a method of placing the supports on which the electrochromic layers have been formed facing each other with a gap of 5 μm to 150 μm maintained, filling the composition solution, and then polymerizing it by ultraviolet irradiation or heating can be used.

[0066] [Electrochromic layer] The first electrochromic layer 3 and the second electrochromic layer 5 are layers containing an electrochromic material, and are disposed on the upper and lower surfaces of the electrolyte layer 4 so as to sandwich the electrolyte layer 4 therebetween.

[0067] The following describes the case where the second electrochromic layer 5 contains metal nanoparticles and an electrochromic material. However, even if the first electrochromic layer 3 contains metal nanoparticles and an electrochromic material, the other configurations, effects, etc. are similar, although the oxidation-reduction action is different.

[0068] (Metal Nanoparticles) Metal nanoparticles have excellent electrical conductivity and can conduct electricity through electrochromic materials. The metal nanoparticles may be any conductive metal particles, and specifically, for example, one or more kinds selected from tin oxide, titanium oxide, zinc oxide, antimony (V) oxide, zirconium oxide, and yttrium oxide may be mentioned. Among them, tin oxide and titanium oxide are preferable.

[0069] The average primary particle diameter (hereinafter also referred to as "particle diameter") of the metal nanoparticles is preferably from 1 nm to 100 nm, and more preferably from 3 to 8 nm. By setting the particle size to the above lower limit or more, good color development and decolorization performance can be obtained. On the other hand, by setting the particle size to the above upper limit or less, the transparency of the second electrochromic layer 5 can be maintained, and the specific surface area can be increased, thereby increasing the amount of electrochromic material carried.

[0070] The electrochromic material carried by the metal nanoparticles may be one or more compounds.

[0071] The second electrochromic layer 5 is preferably formed from a sol solution of metal nanoparticles, which can provide a good haze value and increase the reflectance.

[0072] (Electrochromic Materials) The electrochromic material is composed of an electrochromic compound that undergoes an oxidation-reduction reaction when a voltage is applied, and can reversibly develop and decolorize.

[0073] The electrochromic material may be either an inorganic electrochromic compound or an organic electrochromic compound, and known electrochromic compounds such as dye-based, polymer-based, metal complex-based, and metal oxide-based compounds can be used.

[0074] The electrochromic material may be either an inorganic electrochromic compound or an organic electrochromic compound, or a conductive polymer known to exhibit electrochromism. The first electrochromic layer 3 and the second electrochromic layer 5 can be appropriately selected from these electrochromic materials, but when one of them is an electrochromic material having oxidative coloring properties, it is preferable that the other is an electrochromic material having reductive coloring properties. As the electrochromic material having oxidative coloring properties, a polymer obtained by polymerizing an oxidative coloring electrochromic composition containing a radical polymerizable compound is preferable, and an electrochromic composition containing a radical polymerizable compound having triarylamine is particularly preferable.

[0075] The length of a single molecule of the electrochromic material is preferably 5 nm or less.

[0076] (First electrochromic layer) The first electrochromic layer 3 contains, as a main material, an electrochromic material that exhibits color through an oxidation reaction, and is a layer that is colored thereby.

[0077] The average thickness of the first electrochromic layer 3 is not particularly limited, but is preferably about 0.1 μm or more and 30 μm or less, and more preferably about 0.4 μm or more and 10 μm or less.

[0078] The electrochromic material contained as the main material in the first electrochromic layer 3 and which exhibits color through an oxidation reaction is not particularly limited, and examples thereof include a polymer obtained by polymerizing a composition containing a radically polymerizable compound having a triarylamine, a bisacridan compound, a Prussian blue complex, and nickel oxide, and one or more of these may be used in combination.

[0079] Examples of polymers obtained by polymerizing a composition containing a radically polymerizable compound having a triarylamine include those described in JP-A-2022-25243, JP-A-2016-45464, and JP-A-2020-138925.

[0080] Furthermore, an example of a Prussian blue-type complex is a material made of Fe(III)4[Fe(II)(CN)6]3.

[0081] Among these, a polymer obtained by polymerizing a composition containing a radically polymerizable compound having triarylamine is preferably used, since it can be operated at a constant voltage, has excellent durability during repeated use, and can provide an electrochromic element with high contrast.

[0082] In addition, the composition containing the radical polymerizable compound having a triarylamine may contain another radical polymerizable compound different from the radical polymerizable compound having a triarylamine, and the polymer obtained by polymerizing such a composition may be composed of a crosslinked product in which these radical polymerizable compounds are crosslinked.

[0083] (Second electrochromic layer) The second electrochromic layer 5 contains, as a main material, an electrochromic material that changes from transparent to colored by a reduction reaction, and is a layer that is colored by this.

[0084] The average thickness of the second electrochromic layer 5 is not particularly limited, but is preferably about 0.2 μm to 5.0 μm, and more preferably about 1.0 μm to 4.0 μm. If the average thickness is less than 0.2 μm, it may be difficult to obtain a desired color density depending on the type of electrochromic material, and if it exceeds 5.0 μm, the manufacturing cost may increase and visibility may decrease due to coloring depending on the type of electrochromic material.

[0085] The second electrochromic layer 5 preferably uses an electrochromic material having the same color tone as the first electrochromic layer 3. This improves the maximum color density, and as a result, the contrast can be improved.

[0086] In contrast, when materials of different colors are used, color mixing becomes possible. In addition, by coloring the first transparent electrode layer 2 and the second transparent electrode layer 6 through oxidation and reduction reactions on both pole sides, the driving voltages in the electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 can be effectively reduced, and the repeated durability of the electrochromic sheet 100 can be improved.

[0087] The electrochromic material contained as the main material in the second electrochromic layer 5 and which exhibits coloration by a reduction reaction is not particularly limited, and examples thereof include inorganic electrochromic compounds, organic electrochromic compounds, conductive polymers, etc., and one or a combination of two or more of these can be used.

[0088] Examples of inorganic electrochromic compounds include tungsten oxide, molybdenum oxide, iridium oxide, titanium oxide, etc., and among these, tungsten oxide is preferred. Tungsten oxide is preferably used because it has a low color development / discoloration potential due to its low reduction potential, and is also excellent in durability because it is an inorganic material.

[0089] In addition, as the organic electrochromic compound, for example, azobenzene-based, anthraquinone-based, diarylethene-based, dihydroprene-based, dipyridine-based, styryl-based, styrylspiropyran-based, spirooxazine-based, spirothiopyran-based, thioindigo-based, tetrathiafulvalene-based, terephthalic acid-based, triphenylmethane-based, triphenylamine-based, naphthopyran-based, viologen-based, pyrazoline-based, phenazine-based, phenylenediamine-based, phenoxazine-based, phenothiazine-based, phthalocyanine-based, fluoran-based, fulgide-based, benzopyran-based, metallocene-based, and other low molecular weight organic electrochromic compounds can be mentioned, among which viologen-based compounds and dipyridine-based compounds are preferred.These compounds are preferably used because they have low color development and fading potential and show good color value.

[0090] Examples of viologen compounds include those described in JP 2022-025243 A, JP 3955641 A, JP 2007-171781 A, etc. Examples of dipyridine compounds include those described in JP 2007-171781 A, JP 2008-116718 A, etc.

[0091] Examples of the conductive polymer include polypyrrole, polythiophene, polyaniline, and derivatives thereof.

[0092] [Transparent base layer (support layer)] The first transparent substrate layer 1 and the second transparent substrate layer 7 have the function of supporting the first transparent electrode layer 2, the first electrochromic layer 3, the electrolyte layer 4, the second electrochromic layer 5, the second transparent electrode layer 6, and the sealing material 8.

[0093] Furthermore, the first transparent substrate layer 1 and the second transparent substrate layer 7 constitute the outermost layers of the electrochromic sheet 100. That is, at least the first electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 are not exposed to the outside. Therefore, the first electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 can be protected from moisture and oxygen gas from the outside, as well as physical impacts, friction, and the like.

[0094] The first transparent substrate layer 1 and the second transparent substrate layer 7 are not particularly limited as long as they are composed mainly of a transparent resin material, but it is preferable that they contain a transparent resin (base resin) having thermoplastic properties as the main material.

[0095] The transparent resin is not particularly limited, but examples thereof include one or more types selected from episulfide-based resins, thiourethane-based resins, acrylic-based resins, polycarbonate-based resins, urethane-based resins, polyamide-based resins, polyester-based resins, cellulose-based resins, cycloolefin polymers (COP), cycloolefin copolymers (COC), norbornene-based resins, and silicone-based resins.

[0096] Among these, polycarbonate-based resins or polyamide-based resins are preferred, and polycarbonate-based resins are particularly preferred. Polycarbonate-based resins are rich in transparency (light transmissivity) and mechanical strength such as rigidity, and also have high heat resistance, so that the use of polycarbonate-based resins as the transparent resin can improve the transparency, impact resistance, and heat resistance of the first transparent substrate layer 1 and the second transparent substrate layer 7.

[0097] As the polycarbonate resin, various resins can be used, among which aromatic polycarbonate resins are preferable. Aromatic polycarbonate resins have aromatic rings in their main chains, which allows the first transparent substrate layer 1 and the second transparent substrate layer 7 to have superior strength.

[0098] The aromatic polycarbonate resin is synthesized, for example, by an interfacial polycondensation reaction between bisphenol and phosgene, or an ester exchange reaction between bisphenol and diphenyl carbonate.

[0099] Examples of bisphenols include bisphenol A and bisphenol (modified bisphenol) which is the source of the repeating unit of polycarbonate represented by the following formula (1A).

[0100] [ka]

[0101] (In formula (1A), X is an alkyl group having 1 to 18 carbon atoms, an aromatic group, or a cyclic aliphatic group; Ra and Rb are each independently an alkyl group having 1 to 12 carbon atoms; m and n are each an integer of 0 to 4; and p is the number of repeating units.)

[0102] Specific examples of bisphenols that are the source of the repeating units of the polycarbonate represented by formula (1A) include 4,4'-(pentane-2,2-diyl)diphenol, 4,4'-(pentane-3,3-diyl)diphenol, 4,4'-(butane-2,2-diyl)diphenol, 1,1'-(cyclohexanediyl)diphenol, 2-cyclohexyl-1,4-bis(4-hydroxyphenyl)benzene, 2,3-biscyclohexyl-1,4-bis(4-hydroxyphenyl)benzene, 1,1'-bis(4-hydroxy-3-methylphenyl)cyclohexane, and 2,2'-bis(4-hydroxy-3-methylphenyl)propane, and any of these may be used alone or in combination of two or more.

[0103] Among them, the polycarbonate resin is preferably a bisphenol-type polycarbonate resin having a skeleton derived from bisphenol as the main component. By using such a bisphenol-type polycarbonate resin, the first transparent substrate layer 1 and the second transparent substrate layer 7 exhibit even greater strength.

[0104] In this embodiment, the absorbance of the second transparent substrate layer 7 at a wavelength of 320 nm is preferably 1 or less, and more preferably 0.8 or less. The absorbance of the second transparent substrate layer 7 at a wavelength of 295 nm is preferably 1 or less, and more preferably 0.8 or less. In this embodiment, the second transparent substrate layer 7 may not contain an ultraviolet absorbing agent. In this case, an ultraviolet ray blocking function can be imparted to eyewear using the electrochromic sheet 100 of this embodiment. On the other hand, in this embodiment, the first transparent substrate layer 1 may contain a known ultraviolet absorbing agent.

[0105] Coloring agents As long as the first transparent substrate layer 1 and the second transparent substrate layer 7 have optical transparency, they may further contain a colorant, and the color may be any color, such as colorless, red, blue, or yellow.

[0106] These colors can be selected by incorporating a colorant such as a dye or a pigment in the first transparent substrate layer 1 and the second transparent substrate layer 7. Examples of the dye include acid dyes, direct dyes, reactive dyes, and basic dyes, and one or more selected from these may be used in combination.

[0107] Specific examples of dyes include CI Acid Yellow 17, 23, 42, 44, 79, 142, CI Acid Red 52, 80, 82, 249, 254, 289, CI Acid Blue 9, 45, 249, CI Acid Black 1, 2, 24, 94, CI Food Black 1, 2, CI Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 14 4,173, CI Direct Red 1, 4, 9, 80, 81, 225, 227, CI Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, CI Direct Black 19, 38, 51, 71, 154, 168, 171, 195, CI Reactive Red 14, 32, 55, 79, 249, CI Reactive Black 3, 4, 35, etc.

[0108] The first transparent substrate layer 1 and the second transparent substrate layer 7 may contain, in addition to the transparent resin, dye, or pigment described above, various additives such as antioxidants, fillers, plasticizers, light stabilizers, ultraviolet absorbers, heat absorbers, and flame retardants, as necessary.

[0109] Moreover, the first transparent substrate layer 1 and the second transparent substrate layer 7 may be stretched or unstretched.

[0110] Furthermore, the refractive index at a wavelength of 589 nm of the first transparent substrate layer 1 and the second transparent substrate layer 7 is preferably 1.3 or more and 1.8 or less, more preferably 1.4 or more and 1.65 or less. By setting the refractive index n1 of the first transparent substrate layer 1 and the second transparent substrate layer 7 within the above numerical range, the color developing and decoloring function of the electrochromic sheet 100 can be easily visually recognized.

[0111] The average thickness of the first transparent substrate layer 1 and the second transparent substrate layer 7 is preferably set to be 0.1 mm or more and 10.0 mm or less, and more preferably 0.3 mm or more and 5.0 mm or less. By setting the average thickness of the first transparent substrate layer 1 and the second transparent substrate layer 7 within this range, it is possible to appropriately suppress or prevent the electrochromic sheet 100 from warping while making the electrochromic sheet 100 thinner.

[0112] The first transparent substrate layer and the second transparent substrate layer 7 may be made of the same or different materials. In addition, both may be stretched, or only one may be unstretched.

[0113] The first transparent substrate layer and the second transparent substrate layer 7 may have the same refractive index or may have different refractive indices. The first transparent substrate layer and the second transparent substrate layer 7 may have the same thickness or may have different thicknesses.

[0114] [Sealing material] The sealing material 8 integrally covers the side surface of the electrolyte layer 4 and the side surfaces of the first electrochromic layer 3 and the second electrochromic layer 5, and is used to prevent moisture and oxygen gas from entering the electrochromic element 10 from the outside, and to adhere to the first transparent substrate layer 1 and the second transparent substrate layer 7 to prevent peeling from the electrochromic element 10. In addition, if the first electrochromic layer 3 and the second electrochromic layer 5 formed between the opposing first transparent electrode layer 2 and second transparent electrode layer 6 are misaligned, the color development quality during operation will decrease, so the sealing material 8 is used to prevent this.

[0115] The average thickness (length in the stacking direction) of the sealing material 8 is adjusted according to the average thickness of the electrochromic elements 10, and is preferably set to about 20 μm or more and 100 μm or less, and more preferably about 40 μm or more and 80 μm or less, for example.

[0116] The sealing member 8 is formed using a sealing material described below.

[0117] (Sealing material) The sealing material in this embodiment is not particularly limited as long as it is an insulating material, but preferably contains a curable resin.

[0118] ·Curable resin The curable resin may be, for example, one or more selected from epoxy resin, acrylic resin, phenol resin, maleimide resin, silicone resin, urethane resin, cyanate resin, melamine resin, urea resin, and unsaturated polyester resin. Those having at least one of an ultraviolet reactive functional group and a heat reactive functional group are preferred, and those having a (meth)acryloyl group and / or an epoxy group are more preferred. The curable resin may, for example, be a thermosetting resin such as (meth)acrylate or epoxy resin.

[0119] The (meth)acrylate is not particularly limited, and examples thereof include urethane (meth)acrylate having a urethane bond, and epoxy (meth)acrylate derived from a compound having a glycidyl group and (meth)acrylic acid.

[0120] The urethane (meth)acrylate is not particularly limited, and examples thereof include derivatives of diisocyanates such as isophorone diisocyanate and reactive compounds that undergo addition reaction with isocyanates such as acrylic acid and hydroxyethyl acrylate. These derivatives may be chain-extended with caprolactone, polyol, etc.

[0121] The epoxy (meth)acrylate is not particularly limited, and examples thereof include those obtained by reacting an epoxy compound with (meth)acrylic acid in the presence of a basic catalyst according to a conventional method, etc. Examples thereof include epoxy (meth)acrylates derived from an epoxy resin such as a bisphenol A type epoxy resin or propylene glycol diglycidyl ether and (meth)acrylic acid.

[0122] Examples of other (meth)acrylates include one or more selected from methyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, (poly)ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and glycerin dimethacrylate.

[0123] Examples of the epoxy resin include novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins, bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, aromatic glycidylamine type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, and aminophenol type glycidylamine, hydroquinone type epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins, triphenolmethane type epoxy resins, triphenolpropane type epoxy resins, and alkyl glycidylamines. Examples of the epoxy resin include one or more selected from epoxy resins such as modified triphenolmethane type epoxy resins, triazine nucleus-containing epoxy resins, dicyclopentadiene modified phenol type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a phenylene and / or biphenylene skeleton, and naphthol aralkyl type epoxy resins having a phenylene and / or biphenylene skeleton; and aliphatic epoxy resins such as alicyclic epoxy resins such as vinylcyclohexene dioxide, dicyclopentadiene oxide, and alicyclic diepoxy adipide.

[0124] The sealing material of the present embodiment may further contain inorganic particles.

[0125] ·Inorganic particles Examples of inorganic particles include one or more types selected from silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, and the like.

[0126] The inorganic particles may be those whose surfaces have been hydrophobically treated. For example, the inorganic particles may be surface-treated by a known method using epoxysilane, aminosilane, (meth)acrylic silane, vinylsilane, methylchlorosilane, dimethylpolysiloxane, etc. The inorganic particles may be used in combination with those that have been hydrophobically treated and those that have not.

[0127] The content of the inorganic particles is from 1 to 80 mass %, preferably from 3 to 70 mass %, and more preferably from 20 to 60 mass %, based on the total amount of the sealing material.

[0128] ·others The sealing material of the present embodiment may contain organic particles, a polymerization initiator, a heat curing agent, and the like in addition to the above-mentioned curable resin and inorganic particles.

[0129] The organic particles may be, for example, one or more types selected from polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, silicone fine particles, core-shell type rubber fine particles, and the like.

[0130] Examples of the polymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.

[0131] Examples of the radical polymerization initiator include a photoradical polymerization initiator which generates radicals upon irradiation with light, and a thermal radical polymerization initiator which generates radicals upon heating.

[0132] Examples of the photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and thioxanthone.

[0133] Examples of the thermal radical polymerization initiator include those made of an azo compound, an organic peroxide, etc. Among them, a polymeric azo initiator made of a polymeric azo compound is preferred.

[0134] As the cationic polymerization initiator, a photocationic polymerization initiator can be suitably used. The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid upon irradiation with light, and may be either an ionic photoacid generating type or a nonionic photoacid generating type. Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts; and organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes.

[0135] The content of the polymerization initiator is preferably 0.1 to 30 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the polymerization initiator is equal to or more than the lower limit, the sealing material has better curability, whereas when the content of the polymerization initiator is equal to or less than the upper limit, the sealing material has better storage stability.

[0136] The heat curing agent is used to react and crosslink the heat-reactive functional groups in the curable resin by heating, and has the role of improving the adhesiveness and moisture resistance of the curable resin composition after curing. Examples of the heat curing agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, etc. Among these, solid organic acid hydrazides are preferably used.

[0137] The content of the above-mentioned heat curing agent is preferably 0.1 to 50 parts by weight, and more preferably 1 to 30 parts by weight, based on 100 parts by weight of the curable resin. When the content of the polymerization initiator is equal to or more than the lower limit, the sealing material has better curability, whereas when the content of the polymerization initiator is equal to or less than the upper limit, the sealing material has better coatability.

[0138] In addition, additives such as a silane coupling agent, a light blocking agent, a reactive diluent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other coupling agents may be contained as necessary.

[0139] (Method of manufacturing sealing materials) An example of a method for producing the sealing material of the present embodiment is a method in which a curable resin, inorganic particles, and additives such as a polymerization initiator and / or a heat curing agent or a silane coupling agent, which are added as necessary, are mixed using a mixer. Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, and a planetary mixer.

[0140] [Columnar conductive part] The first columnar conductive portion 22 is provided as wiring so as to overlap, in a plan view, with the first transparent electrode layer 2 extending from the electrochromic element 10 and to penetrate the sealing material 8 (see FIG. 1). The first columnar conductive portion 22 is electrically connected to the first transparent electrode layer 2 via the first auxiliary electrode layer 21.

[0141] The first columnar conductive portion 22 is exposed at an end of the eyeglass lens when the outer shape of the electrochromic sheet 100 is processed into the shape of an eyeglass lens in order to apply the electrochromic sheet 100 to the eyeglass lens. This allows electricity to be applied to the electrochromic element 10 from the outside via the first columnar conductive portion 22. The second columnar conductive portion 62, like the first columnar conductive portion 22, is exposed at the end of the eyeglass lens when the outer shape of the electrochromic sheet 100 is processed into the eyeglass lens shape in order to apply the electrochromic sheet 100 to the eyeglass lens. This allows electricity to be applied to the electrochromic element 10 from the outside via the second columnar conductive portion 62. In this case, the first columnar conductive portion 22 can be located on the bridge side of the eyeglass lens, and the second columnar conductive portion 62 can be located on the temple side (opposite the bridge side) of the eyeglass lens.

[0142] Furthermore, the first columnar conductive portion 22 and the second columnar conductive portion 62 each independently have an average thickness set to preferably about 10 μm or more and 100 μm or less, more preferably about 20 μm or more and 80 μm or less, and even more preferably about 30 μm or more and 70 μm or less.

[0143] The material for the first columnar conductive portion 22 and the second columnar conductive portion 62 may be a conductive paste having electrical conductivity. This can improve the adhesion between the first columnar conductive portion 22 and the second columnar conductive portion 62 and the sealing material 8.

[0144] (Other electrodes) The first auxiliary electrode layer 21 is provided as wiring by being laminated on the surface of the first transparent electrode layer 2 opposite to the first transparent substrate layer 1, and is electrically connected to the first columnar conductive portion 22. Similarly, the second auxiliary electrode layer 61 is laminated as wiring on the surface of the second transparent electrode layer 6 opposite the second transparent substrate layer 7, and is electrically connected to the second columnar conductive portion 62.

[0145] The resistance values ​​of the first auxiliary electrode layer 21 and the second auxiliary electrode layer 61 are set lower than the resistance values ​​of the first transparent electrode layer 2 and the second transparent electrode layer 6, respectively. Therefore, by forming wiring electrically connected to the electrochromic element 10 with the laminate of the first transparent electrode layer 2 and the first auxiliary electrode layer 21, and the laminate of the second transparent electrode layer 6 and the second auxiliary electrode layer 61, respectively, it is possible to impart superior electrical conductivity to these wirings (laminates).

[0146] The constituent materials of the first auxiliary electrode layer 21 and the second auxiliary electrode layer 61 are not particularly limited as long as they have a lower resistance value than the first transparent electrode layer 2 and the second transparent electrode layer 6, respectively, but materials with excellent conductivity are used, such as silver, aluminum, copper, chromium, and molybdenum, and one or a combination of two or more of these can be used.

[0147] The first auxiliary electrode layer 21 and the second auxiliary electrode layer 61 each have an average thickness preferably set to about 1 nm or more and 100 nm or less, more preferably about 5 nm or more and 50 nm or less, so that the first auxiliary electrode layer 21 and the second auxiliary electrode layer 61 can reliably function as auxiliary electrodes.

[0148] [Electrochromic sheet composition, thickness, etc.] The total thickness of the electrochromic sheet 100 of this embodiment is not particularly limited, but is preferably 0.1 mm or more and 10.0 mm or less, and more preferably 0.3 mm or more and 5.0 mm or less. By making the total thickness of the electrochromic sheet 100 equal to or greater than the above-mentioned lower limit, strength can be maintained, while by making the layer thickness equal to or less than the above-mentioned upper limit, the electrochromic sheet 100 can be easily processed, such as by cutting or bending.

[0149] Each layer of the electrochromic sheet 100 may be replaced with any layer having a similar function, or other layers may be further provided.

[0150] <Manufacturing method of electrochromic sheet> The method for producing the electrochromic sheet 100 includes the following steps. A step of forming a first transparent electrode layer 2 on a first transparent substrate layer 1, and laminating a first electrochromic layer 3 on the first transparent electrode layer 2; forming a second transparent electrode layer 6 on the second transparent substrate layer 7, and forming a second electrochromic layer 5 on the second transparent electrode layer 6; a step of applying a sealing material onto the first transparent electrode layer 2 so as to surround the outer edge of the first electrochromic layer 3, or applying a sealing material onto the second transparent electrode layer 6 so as to surround the outer edge of the second electrochromic layer 5; a step of preparing an electrolyte layer 4, and bonding a first transparent substrate layer 1 and a second transparent substrate layer 2 together, with a first electrochromic layer 3 and a second electrochromic layer 5 facing each other with the electrolyte layer 4 interposed therebetween; curing the sealing material to form a sealing material 8; having In the lamination step, the sealing material is spread out, so that the first electrochromic layer 3 and the second electrochromic layer 5 are covered with the sealing material. In this way, the electrochromic sheet 100 is obtained.

[0151] <Manufacturing method of electrochromic lenses> Next, each step of the manufacturing method of the lens 30 including the curved sheet 120 obtained by curvedly forming the electrochromic sheet 100 of this embodiment will be described in detail. Fig. 2 is a schematic diagram showing a method for manufacturing a lens using the electrochromic sheet of this embodiment. The upper side of Fig. 2 is referred to as "top" and the lower side of Fig. 2 is referred to as "bottom" in the following description. As shown in Fig. 2, the electrochromic sheet 110 has a plurality of electrochromic elements 10 and a sealant 8 surrounding the electrochromic elements 10, in other words, the electrochromic sheet 110 has a plurality of electrochromic elements 10 partitioned by the sealant 8.

[0152] (Process 1) First, protective films 50 (masking tape) are attached to both sides of the electrochromic sheet 110 to obtain a connecting sheet laminate 210 in which the protective films 50 are attached to both sides of the electrochromic sheet 110 (see FIG. 2(a)).

[0153] (Process 2) 2(b), the connecting sheet laminate 210 is punched in its thickness direction so as to correspond to each electrochromic element 10, thereby obtaining an element laminate 250 in which the connecting sheet laminate 210 is singulated into pieces each having a substantially rectangular shape in a plan view. That is, the electrochromic sheet 100 is obtained, singulated into a substantially rectangular shape corresponding to each electrochromic element 10 and the sealing material 9 covering the outer edge thereof with the protective film 50 attached to both sides (see FIG. 1).

[0154] The shape of the individual electrochromic sheet 100 may be any of a variety of shapes, such as a rectangular shape, a circular shape, an elliptical shape, etc. The shape to be adopted may be appropriately selected depending on the final lens 30.

[0155] (Step 3) 2(c), the separated element stack 250 is subjected to a thermal bending process under heating to form the element stack 250 into a curved element stack 220 having a curved shape with one surface side being a curved concave surface and the other surface side being a curved convex surface. This allows the flat electrochromic sheet 100 to be formed into a curved sheet 120 having a curved shape with the protective films 50 attached to both surfaces.

[0156] This heat bending is usually carried out by press forming or vacuum forming. At this time, the heating temperature (molding temperature) of the element stack 250 (electrochromic sheet 100) is preferably set to about 110° C. or higher and 170° C. or lower, and more preferably about 130° C. or higher and 160° C. or lower. By setting the heating temperature within this range, it is possible to prevent alteration or deterioration of the electrochromic sheet 100, while softening or melting the electrochromic sheet 100, and reliably thermally bending the electrochromic sheet 100 into the curved sheet 120 having a curved shape.

[0157] (Step 4) Next, the protective film 50 is peeled off from the curved sheet 120 that has been thermally bent. Thereafter, as shown in FIG. 2(d), the curved concave surface of the mold 40 having a curved concave surface formed in a curved shape is brought into contact with the curved convex surface of the curved sheet 120, and in a state where the curved sheet 120 is adsorbed, a resin layer 35 (molding layer) mainly made of a resin material is injection molded on the curved concave surface of the curved sheet 120 by, for example, insert injection molding. More specifically, in a state where the curved sheet 120 is adsorbed on the lower mold 42, an upper mold 41 is attached, and in a cavity 43 that is a space formed by the lower mold 42 and the upper mold 41, a resin layer 35 mainly made of a resin material is molded by, for example, insert injection molding. That is, the constituent material of the resin layer 35 in a molten state is cooled and solidified while in contact with the curved concave surface of the curved sheet 120, and the resin layer 35 is molded in a state of direct contact with the curved concave surface of the curved sheet 120 without an adhesive layer or the like being interposed therebetween. In this way, the base lens 30 including the thermally bent curved sheet 120 and the resin layer 35 is manufactured.

[0158] When the resin layer 35 is injection molded, the heating temperature (molding temperature) of the constituent material of the resin layer 35 to make it in a molten state is appropriately set according to the type of the constituent material of the resin layer 35, but when the constituent material of the resin layer 35 is the same or identical to the constituent material of the transparent base material layers (first transparent base material layer 1 and second transparent base material layer 7) provided in the curved sheet 120, the heating temperature is preferably set to about 180° C. or higher and 320° C. or lower, more preferably about 230° C. or higher and 300° C. or lower. By setting the heating temperature within this range, the constituent material of the resin layer 35 in a molten state can be reliably supplied to the curved concave surface of the curved sheet 120.

[0159] Among the insert injection molding methods, the injection compression molding method is preferably used. The injection compression molding method involves injecting a resin material for forming the resin layer 35 into the mold 40 at low pressure, and then closing the mold 40 at high pressure to apply a compressive force to the resin material, so that the resin layer 35 as the molded body, and in turn the base lens 30, are less likely to suffer from molding distortion or optical anisotropy due to the local orientation of the resin molecules during molding, and is therefore preferably used. Furthermore, by controlling the mold compression force that is uniformly applied to the resin material, the resin material can be cooled at a constant specific volume, so that the resin layer 35 can be obtained with high dimensional accuracy.

[0160] Then, a trimming process is performed to cut the edge of the manufactured base lens 30. In this way, an electrochromic lens of a desired shape can be obtained.

[0161] <Electrochromic lenses> The electrochromic lens of this embodiment is obtained by using the electrochromic sheet 100 described above.

[0162] <Electrochromic device> The electrochromic device of the present embodiment has the electrochromic lens described above, and further has other means as necessary. The other means are not particularly limited and can be appropriately selected depending on the application, and examples thereof include a power source, a fixing means, and a control means. Examples of electrochromic devices include eyewear, photochromic glasses, binoculars, opera glasses, bicycle goggles, watches, electronic paper, electronic albums, electronic billboards, and anti-glare mirrors for automobiles.

[0163] Although the embodiments of the present invention have been described above with reference to the drawings, these are merely examples of the present invention, and various configurations other than those described above can also be adopted. EXAMPLES

[0164] Next, the present invention will be described in detail with reference to examples, but the contents of the present invention are not limited to the examples.

[0165] (1) Preparation of sealing material The following sealing materials were prepared: Sealing material 1: epoxy acrylate resin ("Photolec S-WF17" manufactured by Sekisui Material Solutions Co., Ltd.), no heat treatment

[0166] (2) Preparation of electrochromic sheet <Example 1> An electrochromic sheet as shown in FIG. 1 was produced by the following procedure. - Formation of the first transparent electrode layer - As a first support, a polycarbonate resin substrate (Polycaace, deflection temperature under load 140° C., manufactured by Sumitomo Bakelite Co., Ltd.) having a thickness of 0.5 mm was prepared. An ITO film was formed on the first support by sputtering to a thickness of about 50 nm, and a silver alloy was laminated thereon to a thickness of 5 nm, and another ITO film was laminated thereon to a thickness of 50 nm to form a multilayer (IAI) to form a first transparent electrode layer. Separately, 3 g of titanium oxide (ST-21, Ishihara Sangyo Kaisha), 0.2 g of acetylacetone, and 0.3 g of a surfactant (polyoxyethylene octylphenyl ether, Wako Pure Chemical Industries, Ltd.) were treated in a bead mill together with 5.5 g of water and 1.0 g of ethanol for 12 hours. 1.2 g of polyethylene glycol (#20,000, NOF Corporation) was added to the resulting dispersion to prepare a paste. The obtained paste was applied onto the first transparent electrode layer by screen printing to a thickness of 2 μm, dried at 80°C, and then subjected to UV ozone treatment at 90°C for 20 minutes to form an electron transport layer composed of a porous titanium oxide particle film.

[0167] - Formation of the first electrochromic layer - Next, a 2,2,3,3-tetrafluoropropanol solution containing 1.5 mass % of a reductively coloring electrochromic compound I represented by the following chemical formula was applied by spin coating, and then annealed at 80°C for 10 minutes to support (adsorb) the compound on the porous titanium oxide particle film, thereby forming a first electrochromic layer.

[0168] [ka]

[0169] - Formation of the second transparent electrode layer - A polycarbonate resin substrate of the same shape and thickness as the first support was prepared as the second support. As in the case of the first transparent electrode, an ITO film was formed on the second support by sputtering to a thickness of about 50 nm, and a silver alloy was layered on top of that to a thickness of 5 nm, and an ITO film was layered on top of that to form a multilayer (IAI) to form a second transparent electrode layer.

[0170] - Formation of the second electrochromic layer - On the second transparent electrode layer, polyethylene glycol diacrylate (PEG400DA, manufactured by Nippon Kayaku Co., Ltd.) and a photoinitiator (IRGACURE 184, manufactured by BASF) A solution was prepared by mixing a radical polymerizable compound II having a triarylamine represented by the following formula as an oxidative coloring electrochromic material and 2-butanone in a mass ratio of (57:3:140:800). The prepared solution was then applied to an ITO glass substrate by spin coating.

[0171] [ka] (In the formula, Me represents a methyl group.)

[0172] Next, under a nitrogen atmosphere, a patterned second electrochromic layer having a thickness of 1.2 μm and containing the compound represented by the radical polymerizable compound II above was selectively formed on the second transparent electrode layer by UV curing via a quartz substrate having a patterned Cr layer.

[0173] -Preparation of gel electrolyte- A polymerizable material (V3877, Daido Chemical Industry Co., Ltd.) and an electrolyte (1-ethyl-3-methylimidazolium tetracyanoborate (EMIMTCB)) were mixed in a mass ratio of 20:80 on the surface of a release-treated PET film (NP75C, PANAC Corporation), and a solution in which a photopolymerization initiator (irgacure184, Nippon Kayaku Co., Ltd.) was mixed at 0.5 mass% relative to the polymerizable material was applied. The film was then bonded to a release-treated PET film (NP75A, PANAC Corporation), and cured with ultraviolet (UV) light to produce a gel electrolyte.

[0174] -Lamination process- The release film was peeled off from the prepared gel electrolyte, and the gel electrolyte was attached to the surface of the first electrochromic layer. Next, the prepared sealing material 1 was applied by a dispenser method so as to surround the periphery of the side surface of the first electrochromic layer. Thereafter, the second electrochemical layer of the second support and the surface of the gel electrolyte are aligned and laminated together, and the sealing material is spread to cover the sides of the first electrochemical layer and the second electrochemical layer with the sealing material, and ultraviolet rays are applied at 3 J / cm. 2 The sealing material was cured by irradiation (pre-curing) and then heat curing treatment (main curing) at 100°C for 1 hour to form sealing portions, thereby producing an electrochromic sheet.

[0175] <Example 2> An electrochromic sheet was produced in the same manner as in Example 1, except that the first transparent electrode layer in Example 1 was formed by depositing an ITO film to a thickness of about 100 nm by sputtering.

[0176] <Example 3> An electrochromic sheet was produced in the same manner as in Example 1, except that the first transparent electrode layer and the second transparent electrode layer in Example 1 were formed by depositing an ITO film to a thickness of about 130 nm by a sputtering method.

[0177] <Comparative Example 1> An electrochromic sheet was produced in the same manner as in Example 1, except that the first transparent electrode layer and the second transparent electrode layer in Example 1 were formed by depositing an ITO film to a thickness of about 100 nm by a sputtering method.

[0178] (3) Measurement and evaluation Next, the following measurements and evaluations were carried out on the obtained electrochromic sheet. The results are shown in Table 1.

[0179] [Optical properties] The surface of each electrochromic sheet on the side of the first support layer was irradiated with light from a D65 light source at an incident angle of 90°, and the reflected light was measured using a spectrophotometer at a viewing angle of 10°. The reflectance (%) and the CIE1976L standard deviation of the reflected light were then measured. * a * b * L in chromaticity coordinates * Value a * Value b * The values ​​were calculated respectively. Similarly, the surface of each electrochromic sheet facing the first support layer was irradiated with light from a D65 light source at an incident angle of 90°, and the transmitted light was measured using a spectrophotometer at a viewing angle of 10°. The transmittance (%) and the CIE 1976L standard deviation (DQD) of the reflected light were then measured. * a * b * L in chromaticity coordinates * Value a * Value b * The values ​​were calculated respectively. ·Spectrophotometer “V-670” manufactured by JASCO Corporation

[0180] [Deformation amount] Using each of the obtained electrochromic sheets, a test piece (maximum length 20 mm or more) was prepared with the electrolyte layer in the center and the sealing material on the outer edge, and both ends of the test piece were chucked with the chucking parts, and the center of the test piece was pressed with 30 N for 30 seconds. The difference in depth between the center of the test piece before and after pressing was determined, and this was recorded as the deformation amount (mm).

[0181] [Reflected color and transparency (freedom of design)] Under sunny sunlight, a skilled technician picked up each electrochromic sheet and looked through it, and evaluated the "reflective color" and "transparency" of the electrochromic sheets according to the following criteria. A: Very good. There is no sense of discomfort as a pair of eyeglass lenses. B: It feels a little strange, but there is no problem using it as a spectacle lens. C: It is clearly strange for a eyeglass lens.

[0182] [Table 1] [Explanation of symbols]

[0183] 1 First transparent base layer 2 First transparent electrode layer 3 First electrochromic layer 4 Electrolyte layer 5 Second electrochromic layer 6 Second transparent electrode layer 7 Second transparent base layer 8. Encapsulating materials 10 Electrochromic elements 21 Auxiliary electrode layer 22 Columnar conductive part 30 Raw Lens 35 Resin layer 40 Mold 41 Upper mold 42 Lower mold 50 Protective Film 61 Auxiliary electrode layer 62 Columnar conductive part 100 Electrochromic Sheet 110 Electrochromic Sheet 120 Curved Sheet 210 Connecting sheet laminate 220 Curved element stack 250 Element Stack

Claims

1. a support layer; an electrolyte layer provided on the support layer; an electrochromic layer provided on at least one surface of the electrolyte layer; a pair of transparent electrode layers positioned on the support layer so as to sandwich the electrolyte layer and the electrochemical layer; The electrochromic sheet is configured to satisfy the following condition 1. (Condition 1) The surface of the electrochromic sheet facing the support layer is irradiated with light from a D65 light source at an incident angle of 90°, and the resulting reflected light is measured using a spectrophotometer at a viewing angle of 10°. The CIE 1976L ＊ a ＊ b ＊ a in chromaticity coordinates ＊ is -15 to 15, and b ＊ is between -20 and 10.

2. 2. The electrochromic sheet according to claim 1, An electrochromic sheet configured to further satisfy the following condition 2. (Condition 2) The surface of the electrochromic sheet facing the support layer is irradiated with light from a D65 light source at an incident angle of 90°, and the resulting reflected light is measured using a spectrophotometer at a viewing angle of 10°. The CIE 1976L ＊ a ＊ b ＊ L in chromaticity coordinates ＊ is between 20 and 50.

3. 3. The electrochromic sheet according to claim 1 or 2, An electrochromic sheet configured to further satisfy the following condition 3. (Condition 3) The electrochromic sheet has a transmittance of 70 to 99% when the surface thereof facing the support layer is irradiated with light from a D65 light source at an incident angle of 90° and the transmitted light is measured using a spectrophotometer at a viewing angle of 10°.

4. 3. The electrochromic sheet according to claim 1 or 2, a sealing material on the support layer that covers side surfaces of the electrolyte layer and the electrochemical layer; An electrochromic sheet configured to further satisfy the following condition 4. (Condition 4) Using the electrochromic sheet, a test piece (maximum length of 20 mm or more) is prepared with the electrolyte layer at the center and the sealing material at the outer edge, and both ends of the test piece are chucked with chucking parts, and the center of the test piece is pressed with 30 N for 30 seconds, and the difference in depth between the center of the test piece before pressing and the center of the test piece after pressing is taken as the deformation amount (mm). The deformation amount is 0.01 mm to 0.09 mm.

5. 3. The electrochromic sheet according to claim 1 or 2, The electrochromic sheet, wherein the transparent electrode layer has a thickness of 40 to 200 nm.

6. 3. The electrochromic sheet according to claim 1 or 2, An electrochromic sheet, wherein at least one of the pair of transparent electrode layers has a multilayer structure.

7. 3. The electrochromic sheet according to claim 1 or 2, The electrochromic sheet, wherein the transparent electrode layer contains one or more materials selected from the group consisting of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), zinc-doped indium oxide (IZO), silver (Ag), and a silver alloy, as well as polypyrrole, polyaniline, polythiophene, poly(p-phenylene), polyfluorene, and derivatives thereof.

8. 3. The electrochromic sheet according to claim 1 or 2, The electrochromic sheet has a single-layer or multi-layer structure, and the transparent electrode layer is made of a material selected from tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), zinc-doped indium oxide (IZO), silver (Ag), a silver alloy, and polypyrrole, polyaniline, polythiophene, poly(p-phenylene), polyfluorene, and derivatives thereof.

9. 3. The electrochromic sheet according to claim 1 or 2, An electrochromic sheet, wherein the pair of transparent electrode layers are made of different materials.

10. 3. The electrochromic sheet according to claim 1 or 2, An electrochromic sheet, wherein the pair of transparent electrode layers are made of the same material.

11. 3. The electrochromic sheet according to claim 1 or 2, The electrochromic sheet includes a support layer containing one or more resins selected from episulfide-based resins, thiourethane-based resins, acrylic-based resins, polycarbonate-based resins, urethane-based resins, polyamide-based resins, polyester-based resins, cellulose-based resins, cycloolefin polymers (COP), cycloolefin copolymers (COC), norbornene-based resins, and silicone-based resins.

12. An electrochromic sheet according to claim 1 or 2, The electrochromic sheet, wherein the transparent electrode layer has a thickness of 100 to 200 nm.

13. The electrochromic sheet according to claim 1 or 2, The electrochromic sheet has a transparent electrode layer containing tin-doped indium oxide (ITO), and one or more materials selected from the group consisting of fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), zinc-doped indium oxide (IZO), silver (Ag), a silver alloy, and polypyrrole, polyaniline, polythiophene, poly(p-phenylene), polyfluorene, and derivatives thereof.

14. An electrochromic device using the electrochromic sheet according to claim 1 or 2.

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