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 oxidation-reduction reaction occurs when a voltage is applied, resulting in a reversible change in transmittance. For example, an electrochromic element can be colored by applying a positive voltage, and can be decolored and made transparent by applying a negative voltage. Therefore, by providing a switch that can switch between applying a positive voltage and a negative voltage, the electrochromic element can be colored and decolored at any time.

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

[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 made of ITO and a dimming layer disposed between the pair of transparent electrode layers. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2022-176332 Summary of the Invention [Problem to be solved by the invention]

[0006] Conventionally, electrochromic elements such as those 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 rise in interest in electrochromic elements and the advancement of technology, there is a demand for lenses for eyewear and the like that utilize electrochromic elements to be able to be designed with high precision to achieve a desired color.

[0007] The present inventors have conducted extensive research to increase the degree of freedom in color design, and have found that the conventional technology disclosed in Patent Document 1, even if it has good light transmittance, leaves room for improvement in terms of the degree of freedom in 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] As a result of extensive research into improving the freedom of color design, the inventor devised a new index for controlling the slightly yellowish reflected light, and discovered that it is effective to design an electrochromic sheet to satisfy this index, thereby completing the present invention.

[0009] According to the present invention, the following electrochromic sheet and related technology 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 positioned on the support layer so as to sandwich the electrolyte layer and the electrochemical layer; An electrochromic sheet comprising the above, 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 CIE 1976L * a * b * a in chromaticity coordinates * is -15 to 15, and b * is between -20 and 10. [2] The electrochromic sheet according to [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 reflected light is measured using a spectrophotometer at a viewing angle of 10°. The CIE 1976L * a * b * L in chromaticity coordinates * is 20 to 50. [3] The electrochromic sheet according to [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 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] 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 configured to further 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, and both ends of the test piece are chucked with chucks, 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 and after pressing is taken as 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 multilayer structure. [7] An electrochromic sheet according to any one of [1] to [6], An 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 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] 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 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 device using the electrochromic sheet according to any one of [1] to

[11] . [Effects of the Invention]

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

[0012] [Figure 1] 1 is a schematic cross-sectional view showing an example of an electrochromic sheet according to an embodiment of the present invention. [Figure 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 INVENTION

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

[0014] In this specification, the notation "a to b" in the description of a range of values ​​means a to b, unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass to 5% by mass." Furthermore, the lower and upper limits of a range of values ​​can be arbitrarily combined with the lower and upper limits of other ranges of values.

[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.

[0016] In this embodiment, "covering" is not limited to being continuous, but may also mean that there may be 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 this order, a sealing material 8 that covers 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) that sandwich the top and bottom surfaces of the electrochromic element 10 and the sealing material 8. 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 stacked in this order 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 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 comprises 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) and sandwiching 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 first columnar conductive portions 22 and second columnar conductive portions 62 that penetrate the sealing material 8 in the thickness direction. Both the first columnar conductive portions 22 and the second columnar conductive portions 62 are electrically connected to the electrolyte layer 4. 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 where 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 Figure 1 shows a portion of the electrochromic sheet 100, focusing on a single electrochromic element 10 and the sealing material 9 surrounding it, the electrochromic sheet 100 may also be one in which multiple electrochromic elements 10 are separated by sealing material 8 covering 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 that use it. That is, in the prior art, it was sometimes impossible to obtain the 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 tint, making it easier to obtain a desired color tint. 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 CIE 1976L * a * b * a in chromaticity coordinates * is -15 to 15, and b * is between -20 and 10.

[0024] Although the details of the mechanism by which this effect is obtained are not clear, it is thought that the a * value and b * By controlling the value, it is possible to highly control the apparent color of the electrochromic sheet 100, thereby obtaining a desired color and increasing the degree of freedom in 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 -20 to 10, preferably -15 to 5, and more preferably -10 to 0.

[0026] The electrochromic sheet 100 of this embodiment is further configured to satisfy the following condition 2. This allows for more precise improvement in the degree of freedom in designing the color of the electrochromic sheet 100 and lenses and the like that use it.

[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 20 to 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 this embodiment is further configured to satisfy the following condition 3. This allows for more precise improvement in the degree of freedom in designing the color of the electrochromic sheet 100 and lenses and the like that use it.

[0030] (Condition 3) When the surface of the electrochromic sheet 100 facing 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 facing 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, under 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° and the reflected light may be measured.

[0034] The electrochromic sheet 100 of this embodiment is further configured to satisfy the following condition 4. This allows for more precise improvement in the degree of freedom in designing the color of the electrochromic sheet 100 and lenses and the like that use it.

[0035] (Condition 4) A test piece (maximum length 20 mm or more) is prepared using electrochromic sheet 100, with electrolyte layer 4 at the center and sealing material 8 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.

[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, surface processing for making prescription lenses, or 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.

[0039] In the above condition 4, the shape of the test piece is adjusted appropriately depending on 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. If the shape of the test piece is rectangular, it is preferable that one side is 20 mm or more and the other side is 30 mm or more. There is no particular upper limit to the shape of the test piece, as long as it does not protrude from the stage of the measuring device. The central portion is the 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 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 for the sealing material 9, the material and manufacturing procedure for the electrolyte layer 4, the manufacturing procedure and manufacturing conditions for the electrochromic sheet 100, etc. Specifically, examples include using a material other than ITO as the constituent material for the first transparent electrode layer 2 and the second transparent electrode layer 6, or forming a multilayer 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 side. The second transparent electrode layer 6 is provided on the surface of the second electrochromic layer 5 opposite to the electrolyte layer 4 side.

[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. The layer structures of the first transparent electrode layer 2 and the second transparent electrode layer 6 may be the same or different, and may be symmetrical with respect to the electrolytic layer 4.

[0045] The average thickness of the first transparent electrode layer 2 and the second transparent electrode layer 6 is adjusted so as to obtain the electrical resistance value necessary for the oxidation-reduction reaction of the first electrochromic layer 3 and the second electrochromic layer 5, and to improve the degree of freedom in 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 be equal to or greater than the above-mentioned lower limit, the resistance value can be prevented from increasing too much, and the performance of the electrochromic sheet can be maintained. On the other hand, by setting the thickness of the first transparent electrode layer 2 and the second transparent electrode layer 6 to be equal to or less than the above-mentioned upper limit, the transmittance can be prevented from decreasing too much, and the degree of freedom in designing the appearance can be improved. Furthermore, by setting the thickness of the first transparent electrode layer 2 and the second transparent electrode layer 6 to be within the range of equal to or greater than the above-mentioned lower limit and equal to or less than the above-mentioned upper limit, the color of reflected light can be kept transparent, and the degree of freedom in designing the lens can be improved.

[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, the thickness of each is independently set preferably to 50 nm or more and 200 nm or less, more preferably 100 nm or more and 150 nm or less.

[0047] 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 examples thereof include 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, and a combination of one or more of these may be used.

[0050] The constituent materials of the first transparent electrode layer 2 and the second transparent electrode layer 6 may be the same or different. 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 preferably have a single-layer or multilayer structure including a layer 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), silver alloys, and polypyrrole, polyaniline, polythiophene, poly(p-phenylene), polyfluorene, and derivatives thereof. From the viewpoint of enhancing design freedom, it is preferable that 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), the other does not include a layer made of tin-doped indium oxide (ITO). It is more preferable that both include layers made of tin-doped indium oxide (ITO), and it is even more preferable that two or more layers made of tin-doped indium oxide (ITO) are included.

[0052] Examples of methods for producing the first transparent electrode layer 2 and the second transparent electrode layer 6 include vacuum deposition, sputtering, and ion plating. 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 can be used, 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.

[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 selected appropriately depending on the purpose, but it preferably contains a urethane resin unit in terms of the phase separation temperature and film strength of the polymer membrane. Furthermore, the inclusion of a polyethylene oxide (PEO) chain improves compatibility with the electrolyte and increases the phase separation temperature. Furthermore, the inclusion of a polymethyl methacrylate (PMMA) chain, like the inclusion of a PEO chain, improves compatibility with the electrolyte and increases the phase separation temperature.

[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, and supporting salts of acids and alkalis. 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 more of these can be used in combination.

[0058] In addition to these, 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 therefore easy to handle.

[0059] As for the molecular structure of organic ionic liquids, examples of the cationic component include imidazole derivatives such as N,N-dimethylimidazole salt, N,N-methylethylimidazole salt, and N,N-methylpropylimidazole salt; pyridinium derivatives such as N,N-dimethylpyridinium salt and N,N-methylpropylpyridinium salt; and aliphatic quaternary ammonium salts such as trimethylpropylammonium salt, trimethylhexylammonium salt, and triethylhexylammonium salt. Furthermore, in consideration of stability in the atmosphere, it is preferable to use a fluorine-containing compound as the anionic component, 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, dimethyl sulfoxide, 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 being a low-viscosity liquid, it can also 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 forming the solid electrolyte layer 4 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. Furthermore, a photocurable resin is preferred as the polymer resin. This allows the solid electrolyte layer 4 to be formed at a lower temperature and in a shorter time than when a solid electrolyte layer 4 is formed by thermal polymerization or evaporation of a solvent.

[0065] When the electrolyte layer 4 is in a gel state, it can be produced, for example, as follows. The composition solution can be produced by a polymerization reaction using a cast polymerization method or the like, in which a composition solution is first prepared, and then the prepared composition solution is sandwiched between a mold or a film and polymerized. The composition solution can be produced by mixing an electrolytic solution prepared 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 production method, a method can be used in which a composition solution before polymerization is applied to one electrochromic layer and polymerized by ultraviolet irradiation or heating. Also, a method can be used in which the supports on which the electrochromic layers have been formed are placed facing each other with a gap of 5 μm to 150 μm maintained, and the composition solution is filled in, and then polymerized by ultraviolet irradiation or heating.

[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] Below, we will explain 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 the same, 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 specific examples include one or more selected from tin oxide, titanium oxide, zinc oxide, antimony (V) oxide, zirconium oxide, and yttrium oxide. Of these, tin oxide and titanium oxide are preferred.

[0069] The average primary particle diameter (hereinafter also referred to as "particle diameter") of the metal nanoparticles is preferably 1 nm to 100 nm, and more preferably 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, whereas 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 makes it possible to obtain 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 may be 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 made of an electrochromic material having oxidative coloring properties, it is preferable to use an electrochromic material having reductive coloring properties for the other. As the electrochromic material having oxidative coloring properties, a polymer obtained by polymerizing an oxidative coloring electrochromic composition containing a radical polymerizable compound is preferred, and an electrochromic composition containing a radical polymerizable compound having triarylamine is particularly preferred.

[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, which exhibits color upon oxidation reaction, is not particularly limited, and examples thereof include polymers obtained by polymerizing a composition containing a radically polymerizable compound having triarylamine, bisacridan compounds, Prussian blue complexes, 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 particularly preferably used, since it can be operated at a constant voltage, has excellent durability against repeated use, and can provide an electrochromic element with high contrast.

[0082] The composition containing the radical polymerizable compound having a triarylamine may contain a radical polymerizable compound other than the radical polymerizable compound having a triarylamine, and a 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 upon reduction reaction, and is thus a layer that is colored.

[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 sufficient color density depending on the type of electrochromic material. If the average thickness exceeds 5.0 μm, production costs may increase and visibility may be reduced due to coloring depending on the type of electrochromic material.

[0085] The second electrochromic layer 5 preferably uses an electrochromic material of 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] On the other hand, when materials of different colors are used, color mixing becomes possible. Furthermore, by coloring the first transparent electrode layer 2 and the second transparent electrode layer 6 through oxidation and reduction reactions on both polarity sides, the driving voltages in the electrochromic layer 3, electrolyte layer 4, and second electrochromic layer 5 can be effectively reduced, thereby improving the repeated use durability of the electrochromic sheet 100.

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

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

[0089] Examples of the organic electrochromic compound include low molecular weight organic electrochromic compounds such as azobenzene, anthraquinone, diarylethene, dihydroprene, dipyridine, styryl, styrylspiropyran, spirooxazine, spirothiopyran, thioindigo, tetrathiafulvalene, terephthalic acid, triphenylmethane, triphenylamine, naphthopyran, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, phthalocyanine, fluoran, fulgide, benzopyran, and metallocene, among which viologen compounds and dipyridine compounds are preferred. These compounds are preferably used because they have a low color development / discoloration potential and exhibit good color values.

[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 conductive polymers 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] 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. This protects the first electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 from external moisture, oxygen gas, physical impact, 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 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 excellent in transparency (translucency) and mechanical strength such as rigidity, and also have high heat resistance, so by using a polycarbonate-based resin as the transparent resin, the transparency, impact resistance, and heat resistance of the first transparent substrate layer 1 and the second transparent substrate layer 7 can be improved.

[0097] Various resins can be used as the polycarbonate resin, but aromatic polycarbonate resins are preferred. 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 origin of the repeating unit of polycarbonate represented by the following formula (1A).

[0100] [ka]

[0101] (In formula (1A), X represents an alkyl group, aromatic group, or cycloaliphatic group having 1 to 18 carbon atoms; Ra and Rb each independently represent an alkyl group having 1 to 12 carbon atoms; m and n each represent an integer of 0 to 4; and p represents 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 these can be used alone or in combination of two or more.

[0103] Among these, the polycarbonate resin preferably contains, as a main component, a bisphenol-type polycarbonate resin having a skeleton derived from bisphenol. 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 absorber. In this case, the eyewear using the electrochromic sheet 100 of this embodiment can be provided with an ultraviolet blocking function. On the other hand, in this embodiment, the first transparent substrate layer 1 may contain a known ultraviolet absorber.

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

[0106] These colors can be selected by adding a colorant such as a dye or a pigment to the first transparent substrate layer 1 and the second transparent substrate layer 7 . Examples of dyes 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, and 142, CI Acid Red 52, 80, 82, 249, 254, and 289, CI Acid Blue 9, 45, and 249, CI Acid Black 1, 2, 24, and 94, CI Food Black 1 and 2, and CI Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, and 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, as necessary, various additives such as antioxidants, fillers, plasticizers, light stabilizers, ultraviolet absorbers, heat ray absorbers, and flame retardants in addition to the transparent resins, dyes, or pigments described above.

[0109] 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, and 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 fading 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 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 reduce the thickness of the electrochromic sheet 100 while accurately suppressing or preventing bending of the electrochromic sheet 100.

[0112] The first transparent substrate layer and the second transparent substrate layer 7 may be made of the same or different constituent 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 different refractive indices. The first transparent substrate layer and the second transparent substrate layer 7 may have the same thickness or different thicknesses.

[0114] [Sealing material] The sealing material 8 integrally covers the side surfaces of the electrolyte layer 4 and the side surfaces of the first electrochromic layer 3 and the second electrochromic layer 5, preventing moisture and oxygen gas from penetrating into the electrochromic element 10 from the outside, and is used to adhere to the first transparent substrate layer 1 and the second transparent substrate layer 7 to prevent peeling from the electrochromic element 10. Furthermore, 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 deteriorate, 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 element 10, and is set, for example, preferably to about 20 μm or more and 100 μm or less, more preferably to about 40 μm or more and 80 μm or less.

[0116] The sealing member 8 is formed using a sealing material to be described later.

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

[0118] ·Curable resin Examples of the curable resin include 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. Examples of the curable resin include thermosetting resins such as (meth)acrylate and 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, and epoxy (meth)acrylates derived from an epoxy resin such as a bisphenol A 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, alkyl 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 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 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)acrylicsilane, vinylsilane, methylchlorosilane, dimethylpolysiloxane, etc. As inorganic particles, those that have been hydrophobically treated and those that have not may be used in combination.

[0127] The content of the inorganic particles is 1 to 80 mass %, preferably 3 to 70 mass %, and more preferably 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 thermosetting agent, and the like in addition to the curable resin and inorganic particles.

[0129] The organic particles may be one or more 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 that generates radicals upon irradiation with light, and a thermal radical polymerization initiator that 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 these, a polymeric azo initiator made of a polymeric azo compound is preferred.

[0134] As the cationic polymerization initiator, a photo-cationic 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, relative to 100 parts by weight of the curable resin. When the content of the polymerization initiator is equal to or greater 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 thermosetting agent is used to react and crosslink the thermoreactive functional groups in the curable resin by heating, and has the role of improving the adhesiveness and moisture resistance of the cured curable resin composition. 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 thermosetting agent is preferably 0.1 to 50 parts by weight, and more preferably 1 to 30 parts by weight, relative to 100 parts by weight of the curable resin. When the content of the polymerization initiator is equal to or greater than the lower limit, the curability of the sealing material is improved, whereas when the content of the polymerization initiator is equal to or less than the upper limit, the coatability of the sealing material is improved.

[0138] In addition, additives such as a silane coupling agent, a light-shielding 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 material) Examples of a method for producing the sealing material of the present embodiment include a method in which a curable resin, inorganic particles added as needed, and additives such as a polymerization initiator and / or a heat curing agent or a silane coupling agent 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 plan view, with the first transparent electrode layer 2 that extends 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 portions 22 are exposed at the edge 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 portions 22. Like the first columnar conductive portions 22, the second columnar conductive portions 62 are exposed at the edge 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 second columnar conductive portions 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 first columnar conductive portion 22 and the second columnar conductive portion 62 may be made of any conductive paste having electrical conductivity, thereby improving 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 configuring wiring electrically connected to the electrochromic element 10 with a laminate of the first transparent electrode layer 2 and the first auxiliary electrode layer 21, and a 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 (laminated structures).

[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 more of these can be used in combination.

[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, independently of each other, 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 other layer that can exert the same function, or other layers may be further provided.

[0150] <Method for manufacturing electrochromic sheets> The method for manufacturing 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 the first electrochromic layer 3 and the second electrochromic layer 5 facing each other with the electrolyte layer 4 interposed therebetween; curing the sealing material to form a sealing material 8; and In the bonding 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. As a result, the electrochromic sheet 100 is obtained.

[0151] <Electrochromic lens manufacturing method> 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. 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 sealing material 8 that surrounds them, in other words, the electrochromic sheet 110 has a plurality of electrochromic elements 10 partitioned by the sealing material 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 having a substantially rectangular shape in plan view. That is, with protective films 50 attached to both sides, an electrochromic sheet 100 is obtained that is singulated into a substantially rectangular shape corresponding to each electrochromic element 10 and the sealing material 9 covering the outer edges thereof (see FIG. 1).

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

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

[0156] This heat bending is usually carried out by press forming or vacuum forming. The heating temperature (forming temperature) of the element stack 250 (electrochromic sheet 100) at this time is preferably set to about 110° C. or higher and 170° C. or lower, more preferably about 130° C. or higher and 160° C. or lower. By setting the heating temperature within this range, the electrochromic sheet 100 can be softened or melted while preventing alteration or deterioration of the electrochromic sheet 100, and the electrochromic sheet 100 can be reliably thermally bent to form the curved sheet 120 having a curved shape.

[0157] (Step 4) Next, the protective film 50 is peeled off from the thermally bent curved sheet 120. Thereafter, as shown in Fig. 2(d), a mold 40 having a curved concave surface formed into a curved shape is placed in contact with the curved convex surface of the curved sheet 120, and with the curved sheet 120 adsorbed to the mold 40, a resin layer 35 (molded layer) mainly made of a resin material is injection molded onto the curved concave surface of the curved sheet 120 using, for example, insert injection molding. More specifically, with the curved sheet 120 adsorbed to the lower mold 42, an upper mold 41 is attached, and with, for example, insert injection molding, a resin layer 35 mainly made of a resin material is molded into a cavity 43, which is a space formed by the lower mold 42 and the upper mold 41. 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 direct contact with the curved concave surface of the curved sheet 120 without an adhesive layer or the like 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 injection molding this resin layer 35, the heating temperature (molding temperature) of the constituent material of the resin layer 35 to bring it into a molten state is set appropriately depending on the type of 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 substrate layers (first transparent substrate layer 1 and second transparent substrate layer 7) provided in the curved sheet 120, the 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 insert injection molding methods, injection compression molding is preferably used. Injection compression molding involves injecting a resin material for forming resin layer 35 into mold 40 at low pressure, and then closing mold 40 at high pressure to apply a compressive force to the resin material. This method is therefore preferred because it is less likely to cause molding distortion in resin layer 35 as a molded body, and ultimately in base lens 30, or optical anisotropy due to the local orientation of resin molecules during molding. Furthermore, by controlling the mold compression force applied uniformly to the resin material, it is possible to cool the resin material at a constant specific volume, thereby obtaining a resin layer 35 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 having 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 this embodiment has the above-described electrochromic lens, 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 other configurations can also be adopted. [Example]

[0164] Next, the present invention will be described in detail with reference to examples, but the content of the present invention is 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 (Polyca Ace, 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 approximately 50 nm, and then a silver alloy was layered on top of that to a thickness of 5 nm, and another ITO film was layered on top of that 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, manufactured by Ishihara Sangyo Kaisha), 0.2 g of acetylacetone, and 0.3 g of a surfactant (polyoxyethylene octylphenyl ether, manufactured by 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, manufactured by NOF Corporation) was added to the resulting dispersion to prepare a paste. The obtained paste was applied to 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 made 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 with the first transparent electrode, an ITO film was formed on the second support by sputtering to a thickness of approximately 50 nm. A silver alloy film was then deposited on top of this to a thickness of 5 nm, and another ITO film was then deposited 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 color-developing electrochromic material with 2-butanone in a mass ratio of 57:3:140:800. The solution was then applied to an ITO glass substrate by spin coating.

[0171] [ka] (wherein Me represents a methyl group)

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

[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 onto the surface of a release-treated PET film (NP75C, PANAC Corporation). A solution containing 0.5 mass% of a photopolymerization initiator (irgacure184, Nippon Kayaku Co., Ltd.) was then applied to the surface of the release-treated PET film (NP75A, PANAC Corporation). The solution was then 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 bonded 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 light is applied at 3 J / cm. 2 The sealing material was cured by irradiation (pre-curing) and then subjected to a heat curing treatment (main curing) at 100°C for 1 hour to form a sealing portion, 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 ITO films to a thickness of about 130 nm by sputtering.

[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 ITO films to a thickness of about 100 nm by sputtering.

[0178] (3) Measurement and evaluation Next, the obtained electrochromic sheet was subjected to the following measurements and evaluations. The results are shown in Table 1.

[0179] [Optical properties] The surface of each electrochromic sheet on the side of the first support layer obtained was irradiated with light from a D65 light source at an incident angle of 90°, and the resulting reflected light was measured using a spectrophotometer at a viewing angle of 10°. The reflectance (%) and the CIE 1976L 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 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 Using each of the obtained electrochromic sheets, a test piece (maximum length of 20 mm or more) was prepared with the electrolyte layer in the center and the sealing material as the outer edge. Both ends of the test piece were chucked with 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 pressing and the center of the test piece after pressing was determined, and this was taken as the deformation amount (mm).

[0181] [Reflected color and transparency (design freedom)] Under bright sunlight, a skilled technician picked up each electrochromic sheet and looked through it, and evaluated the "reflected color tone" and "transparency" of the electrochromic sheet according to the following criteria. A: Very good. There is no discomfort as a spectacle lens. B: It feels a little strange, but there is no problem as a spectacle lens. C: It is clearly strange as 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 material 10 Electrochromic elements 21 Auxiliary electrode layer 22 columnar conductive part 30 Elementary Lens 35 Resin layer 40 molds 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 Connected 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 electrochromic layer; An electrochromic sheet for use in eyewear, comprising: (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 ＊ L* in the chromaticity coordinates is 36.7 or more and 42.3 or less, ＊ is 2.1 or more and 12.6 or less, and b ＊ is between -13.2 and 6.

9.

2. 2. The electrochromic sheet according to claim 1, 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°.

3. 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 electrochromic 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.

4. 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.

5. 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.

6. 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.

7. 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.

8. 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.

9. 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.

10. 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.

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

12. 3. 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.

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

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