Electrochromic lens, electrochromic sheet, and electrochromic device

Abstract

An electrochromic lens (300) comprises: an electrochromic element (10); a sealing material (8) that covers the side surface of the electrochromic element (10); and a pair of transparent base material layers (a first transparent base material layer (1) and a second transparent base material layer (7)) that sandwich the electrochromic element (10) and the sealing material (8). The electrochromic lens (300) satisfies a prescribed requirement a.

Description

Electrochromic lens, electrochromic sheet, and electrochromic device

[0001] The present invention relates to an electrochromic lens, an electrochromic sheet, and an electrochromic device, and more particularly to a method of using an electrochromic lens, an electrochromic sheet, an electrochromic device, and an electrochromic sheet.

[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 of 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 provided between the pair of transparent electrode layers.

[0005] In recent years, lenses have been proposed for use in eyewear such as spectacles and sunglasses, which have on their surfaces optical sheets that include polarizing films or half-mirror layers that can impart design features by selectively reflecting light in specific wavelength ranges.

[0006] Therefore, by applying electrochromic elements as optical sheets to lenses in eyewear such as glasses and sunglasses, it is expected that lenses can be obtained that can be switched between coloring and decoloring at any time using a switch.

[0007] For example, Patent Document 2 discloses an eyewear lens that utilizes an electrochromic element. Specifically, the lens has a sealed cavity filled with an electrochromic composition sandwiched between two transparent layers from above and below, and the periphery of the cavity is sealed with a seal made of an adhesive material.

[0008] JP 2022-176332 A International Publication No. 2017 / 009563

[0009] Conventionally, electrochromic elements such as those disclosed in Patent Document 1 have been used in lenses for eyewear, etc., and therefore, attention has been focused on light transmittance to allow good light transmission. Meanwhile, with the recent increase in interest in electrochromic elements and the rise in the level of technology, lenses for eyewear, etc., using electrochromic elements are required to be able to be designed with a desired color with high precision.

[0010] The present inventors have conducted extensive research to increase the degree of freedom in color design, and have found that even if the conventional technology disclosed in Patent Document 1 has good light transmittance, it still has room for improvement in terms of the degree of freedom in color design due to the slightly yellowish reflected light. They then devised a new index to control this reflected light, and discovered that this problem can be solved by designing an electrochromic sheet to satisfy this index, thereby completing the present invention.

[0011] Furthermore, the inventors have studied the technology disclosed in Patent Document 2 and found that the technology focuses on limiting the width of the seal (sealing material) surrounding the cavity to less than 1,000 micrometers, because the seal narrows the field of view of the lens and is visible to the lens user, reducing visual comfort. This reduces the water barrier and oxygen gas barrier properties of the seal, and therefore may reduce the color development and decolorization performance of the electrochromic sheet, such as color tone, speed, and color development stability.

[0012] The present inventors have embodied new requirements for electrochromic lenses that can provide good appearance while maintaining the performance required of electrochromic lenses, and have completed the first invention.

[0013] Furthermore, the inventors conducted extensive research to improve the freedom of color design, and as a result, devised a new index to control the slightly yellowish reflected light, and discovered that it is effective to design an electrochromic sheet to satisfy this index, thereby completing the second invention.

[0014] According to a first aspect of the present invention, the following electrochromic lens and related techniques are provided.

[0015] [1] An electrochromic lens comprising an electrochromic element, a sealing material covering the side surfaces of the electrochromic element, and a pair of transparent substrate layers sandwiching the electrochromic element and the sealing material, and satisfying the following requirement a: (Requirement a) The length of the inner peripheral edge of the sealing material, measured in orthogonal projection when the sealing material is viewed from the top surface of the electrochromic lens through the transparent substrate layers, is L (mm), and the area of ​​the region occupied by the sealing material is S (mm ２ ), S / L is W (mm), there is a first region where W is less than 1 mm and a second region where W is 1.5 mm or more, and the area of ​​the first region is S1 (mm ２ ), and the area of ​​the second region is S2 (mm ２), S1 / S (percentage) is 50% or more, S2 / S (percentage) is 1 to 40%, and the second region has a length of 4 mm at an arbitrary position on the inner circumferential edge of the sealing material as La, and the area of ​​the region occupied by the sealing material including La is Sa (mm ２) and when Sa / La is Wa (mm), the electrochromic lens includes a region where Wa (mm) is 1.5 mm or more. [2] The electrochromic lens according to [1], wherein the electrochromic lens has a through electrode that penetrates the sealing material in the second region. [3] The electrochromic lens according to [1] or [2], wherein the electrochromic lens has a gripping portion in the second region. [4] The electrochromic lens according to any one of [1] to [3], wherein the sealing material is formed from a resin composition containing a curable resin. [5] The electrochromic lens according to any one of [1] to [4], wherein the electrochromic element is a solid or gel having a layered structure in which an electrolyte layer and an electrochromic layer are stacked. [6] The electrochromic lens according to [5], wherein the electrolyte layer is a solid or gel. [7] The electrochromic lens according to any one of [1] to [6], further comprising an electrode layer between the transparent substrate layer and the electrochromic element. [8] The electrochromic lens according to any one of [1] to [7], wherein the transparent substrate layer contains 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. [9] An electrochromic device using the electrochromic lens according to any one of [1] to [8].

[10] A method for using an electrochromic sheet comprising an electrochromic element, a sealing material covering the side surfaces of the electrochromic element, and a pair of transparent substrate layers sandwiching the electrochromic element and the sealing material, the method comprising a step of processing the electrochromic sheet into an electrochromic lens that satisfies the following requirement b: (Requirement b) The length of the inner peripheral edge of the sealing material, measured in orthogonal projection when the sealing material is viewed from the top surface of the electrochromic lens through the transparent substrate layers, is L (mm), and the area of ​​the region occupied by the sealing material is S (mm. ２ ), S / L is W (mm), there is a first region where W is less than 1 mm and a second region where W is 1.5 mm or more, and the area of ​​the first region is S1 (mm ２ ), and the area of ​​the second region is S2 (mm ２ ), S1 / S (percentage) is 50% or more, S2 / S (percentage) is 1 to 40%, and the second region has a length of 4 mm at an arbitrary position on the inner circumferential edge of the sealing material as La, and the area of ​​the region occupied by the sealing material including La is Sa (mm ２ ) and Sa / La is Wa (mm), the range includes a region where Wa (mm) is 1.5 mm or more.

[0016] According to a second aspect of the present invention, the following electrochromic sheet and related techniques are provided.

[0017] [1] An electrochromic sheet comprising: a support layer, an electrolyte layer provided on the support layer, an electrochromic layer provided on at least one surface of the electrolyte layer, and a pair of transparent electrode layers located on the support layer so as to sandwich the electrolyte layer and the electrochromic layer, the electrochromic sheet being configured to satisfy the following condition 1. (Condition 1) When 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 of the reflected light is ＊ a＊ b ＊ a in chromaticity coordinates ＊ is -15 to 15, and b ＊ is -20 to 10. [2] The electrochromic sheet according to [1], further configured to satisfy the following condition 2: (Condition 2) When 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], further configured to satisfy the following condition 3: (Condition 3) When 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 transmitted light obtained is measured using a spectrophotometer at a viewing angle of 10°, the transmittance is 70 to 99%. [4] The electrochromic sheet according to any one of [1] to [3], further comprising a sealant on the support layer that covers side surfaces of the electrolyte layer and the electrochromic layer, and 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 at the center and the sealing material at 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. 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] An electrochromic sheet according to any one of [1] to [4], 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], wherein at least one of the pair of transparent electrode layers has a multilayer structure. [7] The electrochromic sheet according to any one of [1] to [6], wherein the transparent electrode layer contains one or more materials 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] The electrochromic sheet according to any one of [1] to [6], wherein the transparent electrode layer has a single-layer or multi-layer 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), a silver alloy, and polypyrrole, polyaniline, polythiophene, poly(p-phenylene), polyfluorene, and derivatives thereof. [9] The electrochromic sheet according to any one of [1] to [8], wherein the pair of transparent electrode layers are made of different materials.

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

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

[10] , wherein the support layer contains 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] .

[0018] The present invention provides an electrochromic sheet that can improve the degree of freedom in color design, and also provides an electrochromic lens that can provide a good appearance while maintaining the performance required for an electrochromic lens.

[0019] Fig. 1 is a schematic cross-sectional view showing an example of the electrochromic sheet of the present embodiment. Fig. 2 is a schematic view showing a method for manufacturing a lens using the electrochromic sheet of the present embodiment. Fig. 3 is a schematic plan view and a schematic cross-sectional view of the electrochromic lens of the present embodiment. Fig. 4 is a schematic plan view showing an example in which a gripping portion is provided on the electrochromic lens of the present embodiment.

[0020] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. To avoid complexity, when multiple identical components appear in the same drawing, only one of the components may be labeled with a reference symbol, and not all of the components may be labeled with a reference symbol. All drawings are for illustrative purposes only. The shapes and dimensional ratios of each component in the drawings do not necessarily correspond to actual objects.

[0021] In this specification, the notation "a to b" in the description of a numerical range means from a to b, unless otherwise specified. For example, "1 to 5 mass %" means "1 mass % to 5 mass %." Furthermore, 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.

[0022] Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more.

[0023] In this embodiment, "covering" is not limited to being continuous, but may also mean that there may be some discontinuous portions.

[0024] The electrochromic lens of this embodiment is manufactured to correspond to a desired lens using an electrochromic sheet. First, the electrochromic sheet 100 of this embodiment will be described.

[0025] 1 is a schematic cross-sectional view showing an example of an embodiment of an electrochromic sheet 100. As shown in Fig. 1, the electrochromic sheet 100 includes 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 sealant 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 sealant 8 therebetween.

[0026] 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.

[0027] 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 the first transparent substrate layer 1 (support layer) and sandwiching the electrochromic layer 3, electrolyte layer, and electrochromic layer 5. In this embodiment, the first transparent electrode layer 2 and the second transparent electrode layer 6 are transparent. Note that "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.

[0028] 1 , the electrochromic sheet 100 has a first columnar conductive portion 22 and a second columnar conductive portion 62 that penetrate the sealing material 8 in the thickness direction. Both the first columnar conductive portion 22 and the second columnar conductive portion 62 are electrically connected to the electrolyte layer 4. The first columnar conductive portion 22 penetrates the sealing material 8, reaching from a 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, reaching from a second auxiliary electrode layer 61 provided on the second transparent electrode layer 6 to the first transparent substrate layer 1.

[0029] In this embodiment, the electrochromic sheet 100 is described as an example in which a first electrochromic layer 3 and a second electrochromic layer 5 are laminated on both sides of an electrolyte layer 4, but only one of the electrochromic layers may be present.

[0030] 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 partitioned by sealing material 8 covering the side surfaces of each electrochromic element 10.

[0031] 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 the same. That is, in the prior art, 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 suppress the occurrence of color in the reflected light itself, making it easier to obtain a desired color. Furthermore, the electrochromic sheet 100 of this embodiment can have good processability (mechanical strength).

[0032] (Condition 1) When light from a D65 light source is irradiated at an incident angle of 90° onto the surface of the electrochromic sheet 100 on the side of the first transparent substrate layer 1 (support layer), 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.

[0033] 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 ＊ 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.

[0034] 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.

[0035] 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 the same.

[0036] (Condition 2) When 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 CIE 1976L ＊ a ＊ b ＊ L in chromaticity coordinates ＊ is between 20 and 50.

[0037] In condition 2, L ＊ is 20 to 50, preferably 25 to 45, and more preferably 30 to 40.

[0038] 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 the same.

[0039] (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%.

[0040] In condition 3, the transmittance is 70 to 99%, preferably 75 to 99%, and more preferably 80 to 99%.

[0041] 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%.

[0042] 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.

[0043] 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 the same.

[0044] (Condition 4) Using the electrochromic sheet 100, a test piece (maximum length 20 mm or more) is prepared, with the electrolyte layer 4 at the center and the sealing material 8 at the outer edge. 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. The difference in depth between the center of the test piece before and after pressing is defined as the deformation amount (mm). The deformation amount is 0.01 mm to 0.09 mm.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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. When 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, and it is sufficient that 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.

[0049] In this embodiment, the electrochromic sheet 100 that satisfies the above conditions 1 to 4 can be appropriately adjusted 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. Specific 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 using a multilayer structure.

[0050] Hereinafter, each component of the electrochromic sheet 100 will be described in detail.

[0051] [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 sandwiching the first electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 therebetween.

[0052] 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.

[0053] 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 from each other, and may be symmetrical with respect to the electrolytic layer 4.

[0054] The average thicknesses of the first transparent electrode layer 2 and the second transparent electrode layer 6 are adjusted to obtain the electrical resistance required for the oxidation-reduction reactions of the first electrochromic layer 3 and the second electrochromic layer 5, while also improving design flexibility. The thicknesses of the first transparent electrode layer 2 and the second transparent electrode layer 6 are preferably 40 to 200 nm, more preferably 70 to 175 nm, and even more preferably 100 to 150 nm. By setting the thicknesses 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, excessive increases in resistance can be prevented, and performance as an electrochromic sheet can be maintained. On the other hand, by setting the thicknesses 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, excessive decreases in transmittance can be prevented, improving design flexibility for the appearance. Furthermore, by setting the thicknesses of the first transparent electrode layer 2 and the second transparent electrode layer 6 within the range between the above-mentioned lower limit and the above-mentioned upper limit, the color of reflected light can be maintained transparent, improving design flexibility for the lens.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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).

[0060] 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 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 alloys, and polypyrrole, polyaniline, polythiophene, poly(p-phenylene), polyfluorene, and derivatives thereof. From the viewpoint of improving 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 both include layers made of tin-doped indium oxide (ITO).

[0061] Examples of methods for producing each of the first transparent electrode layer 2 and the second transparent electrode layer 6 include vacuum deposition, sputtering, ion plating, etc. Furthermore, as long as the materials for each of 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.

[0062] [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.

[0063] 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.

[0064] The electrolyte layer 4 includes a binder resin and an electrolyte.

[0065] The binder resin is not particularly limited and can be appropriately selected 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, by containing a polyethylene oxide (PEO) chain, compatibility with the electrolyte can be improved and the phase separation temperature can be increased. Furthermore, by containing a polymethyl methacrylate (PMMA) chain, compatibility with the electrolyte can be improved and the phase separation temperature can be increased, similar to the case of containing a PEO chain.

[0066] 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 thereof include LiClO ４ , LiBF ４ , LiAsF ６ , LiPF ６ , LiCF ３ SO ３ , LiCF ３ COO, KCl, NaClO ３ , NaCl, NaBF ４ , NaSCN, KBF ４ , Mg(ClO ４ ) ２ , Mg(BF ４ ) ２ These may be used alone or in combination of two or more.

[0067] 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.

[0068] As the molecular structure of the organic ionic liquid, 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 BF ４ － , C.F. ３ SO ３ － , P.F. ４ － , (CF ３ SO ２ ) ２ N － etc.

[0069] Such an electrolyte material is preferably an ionic liquid containing any combination of cationic and anionic components.

[0070] 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.

[0071] 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.

[0072] The electrolyte filled as the electrolyte layer 4 may be either solid or liquid, but in addition to the case where the electrolyte is 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.

[0073] 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.

[0074] 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 then the prepared composition solution is sandwiched between a mold or a film and polymerized by a polymerization reaction using 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 optionally mixing the polymerization initiator and other components. Another preparation method can be to apply the composition solution before polymerization to one electrochromic layer and polymerize it by ultraviolet irradiation or heating. Alternatively, 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 and then polymerized by ultraviolet irradiation or heating.

[0075] [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.

[0076] 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.

[0077] (Metal Nanoparticles) Metal nanoparticles have excellent conductivity and can conduct electricity through electrochromic materials. The metal nanoparticles may be any metal particles having conductivity, and specifically include one or more selected from tin oxide, titanium oxide, zinc oxide, antimony (V) oxide, zirconium oxide, and yttrium oxide. Among them, tin oxide and titanium oxide are preferred.

[0078] 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 diameter to the above-mentioned lower limit or more, good color development and decolorization performance can be obtained. On the other hand, by setting the particle diameter to the above-mentioned upper limit or less, the transparency of the second electrochromic layer 5 can be maintained and the amount of electrochromic material carried can be increased by increasing the specific surface area.

[0079] The electrochromic material carried by the metal nanoparticles may be one or more compounds.

[0080] 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.

[0081] (Electrochromic Material) 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.

[0082] 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.

[0083] The electrochromic material may be either an inorganic electrochromic compound or an organic electrochromic compound. A conductive polymer known to exhibit electrochromism may also be used. The first electrochromic layer 3 and the second electrochromic layer 5 may be formed from any of these electrochromic materials. However, when one of the layers is formed from an electrochromic material exhibiting oxidative coloring, it is preferable to use an electrochromic material exhibiting reductive coloring for the other layer. The electrochromic material exhibiting oxidative coloring is preferably a polymer obtained by polymerizing an oxidative coloring electrochromic composition containing a radically polymerizable compound, and particularly preferably an electrochromic composition containing a radically polymerizable compound having a triarylamine.

[0084] The length of a single molecule of the electrochromic material is preferably 5 nm or less.

[0085] (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.

[0086] 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.

[0087] The electrochromic material contained as the main material in the first electrochromic layer 3 and which exhibits coloration by an oxidation reaction is not particularly limited, and examples thereof include a polymer obtained by polymerizing a composition containing a radically polymerizable compound having triarylamine, a bisacridan compound, a Prussian blue complex, and nickel oxide, and one or more of these may be used in combination.

[0088] Examples of polymers obtained by polymerizing a composition containing a radically polymerizable compound having triarylamine include those described in JP-A-2022-25243, JP-A-2016-45464, and JP-A-2020-138925.

[0089] Furthermore, examples of Prussian blue complexes include Fe(III) ４ [Fe(II)(CN) ６ ] ３ Examples of the material include:

[0090] 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.

[0091] 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.

[0092] (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 a layer that is colored thereby.

[0093] 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, the manufacturing cost may increase and, depending on the type of electrochromic material, visibility may be reduced due to coloring.

[0094] 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, resulting in improved contrast.

[0095] On the other hand, when materials of different color tones 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 electrode sides, the driving voltages in the electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 can be effectively reduced, thereby improving the repeated use durability of the electrochromic sheet 100.

[0096] The electrochromic material contained as the main material in the second electrochromic layer 5 and which exhibits coloration through 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.

[0097] 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.

[0098] 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.

[0099] Examples of viologen compounds include those described in JP-A-2022-025243, JP-A-3955641, JP-A-2007-171781, etc. Examples of dipyridine compounds include those described in JP-A-2007-171781, JP-A-2008-116718, etc.

[0100] Examples of conductive polymers include polypyrrole, polythiophene, polyaniline, and derivatives thereof.

[0101] [Transparent Substrate 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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 (light transmissivity) 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.

[0106] Various resins can be used as the polycarbonate-based resin, but aromatic polycarbonate-based resins are preferred among them. Aromatic polycarbonate-based 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.

[0107] 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.

[0108] Examples of bisphenols include bisphenol A and bisphenols (modified bisphenols) which are the origin of the repeating units of polycarbonates represented by the following formula (1A).

[0109]

[0110] (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.)

[0111] 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.

[0112] 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.

[0113] In this embodiment, the absorbance of the second transparent substrate layer 7 at a wavelength of 320 nm is preferably 1 or less, 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, more preferably 0.8 or less. In this embodiment, the second transparent substrate layer 7 may not contain an ultraviolet absorber. In this case, an ultraviolet blocking function can be imparted to eyewear using the electrochromic sheet 100 of this embodiment. Meanwhile, in this embodiment, the first transparent substrate layer 1 may contain a known ultraviolet absorber.

[0114] Colorant The first transparent substrate layer 1 and the second transparent substrate layer 7 may further contain a colorant as long as they have light transmittance, and the color may be colorless or any color such as red, blue, or yellow.

[0115] These colors can be selected by incorporating a colorant such as a dye or a pigment into 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.

[0116] Specific examples of dyes include C.I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. Acid Red 52, 80, 82, 249, 254, 289, C.I. Acid Blue 9, 45, 249, C.I. Acid Black 1, 2, 24, 94, C.I. Food Black 1, 2, C.I. Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173, C.I. Direct Red 1, 4, 9, 80, 81, 225, 227, C.I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. Direct Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. Reactive Red 14, 32, 55, 79, 249, C.I. Reactive Black 3, 4, 35, etc.

[0117] The first transparent substrate layer 1 and the second transparent substrate layer 7 may further contain various additives such as an antioxidant, a filler, a plasticizer, a light stabilizer, an ultraviolet absorber, a heat ray absorber, and a flame retardant, in addition to the transparent resin, dye, or pigment described above, as necessary.

[0118] The first transparent substrate layer 1 and the second transparent substrate layer 7 may be stretched or unstretched.

[0119] 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 to the above numerical range, the color developing and decoloring function of the electrochromic sheet 100 can be easily visually recognized.

[0120] 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, more preferably 0.3 mm or more and 5.0 mm or less. Setting the average thickness of the first transparent substrate layer 1 and the second transparent substrate layer 7 within this range makes it possible to reduce the thickness of the electrochromic sheet 100 while accurately suppressing or preventing the electrochromic sheet 100 from warping.

[0121] The first transparent substrate layer and the second transparent substrate layer 7 may be made of the same constituent material or different materials. In addition, both may be stretched, or only one may be unstretched.

[0122] 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.

[0123] [Sealant] The sealant 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 entering 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 sealant is used to prevent this.

[0124] 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, but is preferably set to, for example, about 20 μm or more and 100 μm or less, more preferably about 40 μm or more and 80 μm or less.

[0125] The sealing member 8 is formed using a sealing material to be described later.

[0126] (Sealing Material) The sealing material of the present embodiment is not particularly limited as long as it is an insulating material, but preferably contains a curable resin.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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, such as an epoxy (meth)acrylate derived from an epoxy resin such as a bisphenol A epoxy resin or propylene glycol diglycidyl ether and (meth)acrylic acid.

[0131] 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.

[0132] 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.

[0133] The sealing material of the present embodiment may further contain inorganic particles.

[0134] Inorganic Particles Examples of inorganic particles include one or more particles 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.

[0135] 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.

[0136] The content of the inorganic particles is 1 to 80% by mass, preferably 3 to 70% by mass, and more preferably 20 to 60% by mass, based on the total amount of the sealing material.

[0137] 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.

[0138] 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.

[0139] Examples of the polymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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 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.

[0144] The content of the polymerization initiator is preferably 0.1 to 30 parts by weight, 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 encapsulating material has superior curability. On the other hand, when the content of the polymerization initiator is equal to or less than the upper limit, the encapsulating material has superior storage stability.

[0145] The thermosetting agent reacts with the thermoreactive functional groups in the curable resin by heating to form crosslinks, and serves to improve the adhesiveness and moisture resistance of the curable resin composition after curing. Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, and acid anhydrides. Among these, solid organic acid hydrazides are preferably used.

[0146] The content of the thermosetting agent is preferably 0.1 to 50 parts by weight, 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 becomes superior. On the other hand, when the content of the polymerization initiator is equal to or less than the upper limit, the coatability of the sealing material becomes superior.

[0147] 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.

[0148] (Method for Producing Encapsulating Material) Examples of a method for producing the encapsulating material of the present embodiment include a method of using a mixer to mix 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 needed. Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, and a rotation-revolution mixer.

[0149] [Columnar conductive portion] The first columnar conductive portion 22 is provided as wiring so as to overlap, in 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.

[0150] The first columnar conductive portions 22 are exposed at the edge of the eyeglass lens when the electrochromic sheet 100 is processed to have the shape of an eyeglass lens in order to apply the electrochromic sheet 100 to the eyeglass lens. This allows current 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 also exposed at the edge of the eyeglass lens when the electrochromic sheet 100 is processed to have the shape of an eyeglass lens in order to apply the electrochromic sheet 100 to the eyeglass lens. This allows current 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 portions 22 can be located on the bridge side of the eyeglass lens, and the second columnar conductive portions 62 can be located on the temple side of the eyeglass lens (the side opposite the bridge side).

[0151] Furthermore, the average thickness of each of the first columnar conductive portion 22 and the second columnar conductive portion 62 is preferably set to approximately 10 μm or more and 100 μm or less, more preferably 20 μm or more and 80 μm or less, and even more preferably 30 μm or more and 70 μm or less.

[0152] 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.

[0153] (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 provided as wiring by being laminated on the surface of the second transparent electrode layer 6 opposite to the second transparent substrate layer 7, and is electrically connected to the second columnar conductive portion 62.

[0154] 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 (laminates).

[0155] 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 may be used in combination.

[0156] 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, which allows the first auxiliary electrode layer 21 and the second auxiliary electrode layer 61 to reliably function as auxiliary electrodes.

[0157] [Configuration, Thickness, etc. of Electrochromic Sheet] The total thickness of the electrochromic sheet 100 of this embodiment is not particularly limited, but is preferably 0.1 mm to 10.0 mm, more preferably 0.3 mm to 5.0 mm. 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 cut, bent, or otherwise processed.

[0158] Each layer of the electrochromic sheet 100 may be replaced with any other layer that can perform the same function, or other layers may be further provided.

[0159] <Method for Manufacturing Electrochromic Sheet> The method for manufacturing the electrochromic sheet 100 includes the following steps. The method includes the steps 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 a second transparent substrate layer 7 and forming a second electrochromic layer 5 on the second transparent electrode layer 6, applying a sealing material to the first transparent electrode layer 2 so as to surround the outer edge of the first electrochromic layer 3 or applying a sealing material to the second transparent electrode layer 6 so as to surround the outer edge of the second electrochromic layer 5, preparing an electrolyte layer 4 and bonding the first transparent substrate layer 1 and the 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, and curing the sealing material to form a sealant 8. In the bonding step, the sealing material is spread out to cover the first electrochromic layer 3 and the second electrochromic layer 5. This results in an electrochromic sheet 100.

[0160] Next, a method for manufacturing the electrochromic lens 300 of this embodiment using an electrochromic sheet will be described. However, the electrochromic sheet used for the electrochromic lens 300 is not limited to the electrochromic sheet 100 described above.

[0161] <Method of Manufacturing Electrochromic Lens> Hereinafter, as an example, each step of a method of manufacturing an electrochromic lens including a curved sheet 120 obtained by curvedly forming the electrochromic sheet 100 will be described in detail.

[0162] 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.

[0163] (Step 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)).

[0164] 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 the 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 edge thereof (see FIG. 1).

[0165] 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.

[0166] 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.

[0167] This heat bending process is usually performed by press molding or vacuum molding. The heating temperature (molding temperature) of the element stack 250 (electrochromic sheet 100) during this process 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 heat bent into a curved sheet 120 having a curved shape.

[0168] (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 with 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 (molding 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 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.

[0169] 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 materials of the transparent substrate layers (first transparent substrate layer 1 and second transparent substrate 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.

[0170] Among insert injection molding methods, injection compression molding is preferably used. Injection compression molding involves injecting a resin material for forming the resin layer 35 into a mold 40 at low pressure, and then closing the 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 the molded resin layer 35, and ultimately in the 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.

[0171] The edges of the manufactured base lens 30 are then trimmed, thereby obtaining an electrochromic lens of the desired shape, with the sealing material 8 as the outer edge and the electrochromic element 10 inside (FIG. 2).

[0172] <Electrochromic Lens> Next, an example of an electrochromic lens will be described with reference to Fig. 3. The electrochromic lens 300 of this embodiment includes an electrochromic element 10, a sealant 8 covering the side surfaces of the electrochromic element 10, and a pair of transparent substrate layers (a first transparent substrate layer 1 and a second transparent substrate layer 7) sandwiching the electrochromic element 10 and the sealant 8, and may satisfy the following requirement a.

[0173] (Requirement a) The length of the inner edge of the sealing material 8 measured in orthogonal projection when the sealing material 8 is viewed from the top surface of the electrochromic lens 300 through the first transparent substrate layer 1 or the second transparent substrate layer 7 is L (mm), and the area of ​​the region occupied by the sealing material 8 is S (mm ２ ), S / L is W (mm), there is a first region where W is less than 1 mm and a second region where W is 1.5 mm or more, and the area of ​​the first region is S1 (mm ２ ), and the area of ​​the second region is S2 (mm ２), S1 / S (percentage) is 50% or more, S2 / S (percentage) is 1 to 40%, and the second region has a length of 4 mm at an arbitrary position on the inner circumferential edge of the sealing material 8 as La, and the area of ​​the region occupied by the sealing material 8 including La is Sa (mm ２ ) and Sa / La is Wa (mm), the range includes a region where Wa (mm) is 1.5 mm or more.

[0174] That is, the electrochromic lens 300 has a predetermined ratio of regions where the width of the sealant 8 located at its outer edge in orthogonal projection is 1 mm or less to regions where it is 1.5 mm or more. This allows the sealant 8 to maintain its moisture and oxygen barrier properties, while reducing degradation of design due to the sealant 8 visible through the first transparent substrate layer 1 or the second transparent substrate layer 7 when the electrochromic lens 300 is used. In other words, by having regions where the sealant 8 is narrow and regions where it is wide, the sealant 8 is less visible in the narrow regions, improving the design of the appearance, while the sealant 8 can better demonstrate its barrier function in the wide regions, so that the electrochromic lens 300 as a whole can easily maintain its performance while achieving a good appearance.

[0175] The orthogonal projection of the electrochromic lens 300 refers to the appearance observed when the electrochromic lens 300 is curved overall and placed on a horizontal plane with the convex portion facing upward, and viewed from a vertical direction.

[0176] In the above requirement a, S1 / S (percentage) is 50% or more, and S2 / S (percentage) is 1 to 40%, and preferably S1 / S (percentage) is 70 to 99%, and S2 / S (percentage) is 1 to 30%.

[0177] In the above requirement a, W (= S / L) is not particularly limited, but is preferably 0.3 to 10 mm, and more preferably 0.8 to 8.0 mm.

[0178] The second region is a region where W is 1.5 mm or more, but W may be 2.0 mm or more, or W may be 3.0 mm or more.

[0179] For example, when the second region is a region where W is 3.0 mm or more, it is preferable that S2 / S (percentage) is 1 to 10%.

[0180] Furthermore, the electrochromic lens 300 preferably has a through electrode (first columnar conductive portion 22 or second columnar conductive portion 62) that penetrates the sealing material 8 in the second region. This makes it possible to maintain the color development and decolorization performance while suppressing deterioration in the appearance of the electrochromic lens 300. The first columnar conductive portion 22 or the second columnar conductive portion 62 will be described in detail below, but they are positioned so as to be exposed at the edge of the eyeglass lens when processed into the eyeglass lens shape. Specifically, this can be the bridge side of the eyeglass lens or the temple side of the eyeglass lens (the side opposite the bridge side). In other words, the second region is preferably located near the connection part with the bridge of the eyeglass lens or near the connection part with the temple of the eyeglass lens.

[0181] Furthermore, the electrochromic lens 300 preferably has a gripping portion in the second region. The gripping portion refers to a groove or protrusion for fitting the electrochromic lens 300 into an eyewear frame, or a groove or protrusion for holding the electrochromic lens 300 before attaching it to the eyewear frame. For example, the electrochromic lens 300 may be attached to the eyewear frame by providing a hole in the top of the frame and fitting a convex gripping portion therein, or may be detachable.

[0182] Furthermore, the number of gripping portions on the electrochromic lens 300 may be one or two or more, and in order to maintain a good design while maintaining a balanced state, it is preferable that the number of gripping portions be two or more and that they be positioned in line-symmetrical positions on the electrochromic lens 300.

[0183] The electrochromic lens 300 preferably has second regions or gripping portions in the 1 to 3 o'clock direction and the 9 to 11 o'clock direction when viewed from the center of the electrochromic lens 300. The 12 o'clock direction is the upward direction when the electrochromic lens 300 is oriented vertically during use.

[0184] Specifically, Fig. 4 shows an example in which gripping portions are provided on the electrochromic lens 300 of this embodiment. Fig. 4(a) shows an example in which gripping portions 70a are provided at the 2 o'clock and 10 o'clock directions when viewed from the center of the electrochromic lens 300. Fig. 4(b) shows an example in which a pair of gripping portions 70b are provided on the top edge of the electrochromic lens 300, at the 1 o'clock and 11 o'clock directions when viewed from the center of the electrochromic lens 300. Fig. 4(c) shows an example in which a pair of gripping portions 70c are provided on the corners of the top edge of the electrochromic lens 300, at the 2 o'clock and 10 o'clock directions when viewed from the center of the electrochromic lens 300.

[0185] The shape of the electrochromic lens 300 in a plan view is not particularly limited and may be any known shape, such as Boston (a rounded inverted triangle), Wellington (an inverted trapezoid with the top side longer than the bottom side), oval (egg-shaped), square (approximately rectangular), or round (circular).

[0186] The electrochromic lens 300 that satisfies the above requirement a can be realized by selecting the sealing material that constitutes the sealing member, devising a manufacturing method for the electrochromic sheet, or devising a trimming method for the base lens.

[0187] <Method of Using Electrochromic Sheet> Next, an example of a method of using an electrochromic sheet will be described. The method of using the electrochromic sheet 100 of this embodiment includes an electrochromic element 10, a sealant 8 covering the side surfaces of the electrochromic element 10, and a pair of transparent substrate layers sandwiching the electrochromic element 10 and the sealant 8, and may include a step of processing the electrochromic sheet 100 into an electrochromic lens 300 that satisfies the following requirement b.

[0188] (Requirement b) The length of the inner peripheral edge of the sealing material 8 measured in orthogonal projection when the sealing material 8 is viewed from the top surface of the electrochromic lens 300 through the first transparent substrate layer 1 or the second transparent substrate layer 7 is L (mm), and the area of ​​the region occupied by the sealing material 8 is S (mm ２ ), S / L is W (mm), there is a first region where W is less than 1 mm and a second region where W is 1.5 mm or more, and the area of ​​the first region is S1 (mm ２ ), and the area of ​​the second region is S2 (mm ２ ), S1 / S (percentage) is 50% or more, S2 / S (percentage) is 1 to 40%, and the second region has a length of 4 mm at an arbitrary position on the inner circumferential edge of the sealing material 8 as La, and the area of ​​the region occupied by the sealing material 8 including La is Sa (mm ２ ) and Sa / La is Wa (mm), the range includes a region where Wa (mm) is 1.5 mm or more.

[0189] The process of processing into the electrochromic lens 300 can be carried out by using a known method, for example, by punching out the electrochromic sheet 110 containing the electrochromic elements 10 partitioned by the sealing material 9 into the desired shape, or by further trimming the outer edge of the base lens 30 containing the electrochromic elements 10 punched out into the desired shape and having the sealing material 9 on its outer edge.

[0190] Requirement b can be set and controlled in the same manner as requirement a above.

[0191] According to the method for using the electrochromic sheet 100 of this embodiment, it is possible to obtain an electrochromic lens 300 that has a good appearance while maintaining color development and decolorization performance.

[0192] <Electrochromic Device> The electrochromic device of this embodiment includes at least one of the electrochromic sheet and the electrochromic lens, and further includes 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. Specific examples of electrochromic devices include eyewear, photochromic glasses, smart glasses, binoculars, opera glasses, bicycle goggles, watches, electronic paper, electronic albums, electronic billboards, and anti-glare mirrors for automobiles.

[0193] 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.

[0194] 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.

[0195] (1) Preparation of sealing materials The following sealing materials were prepared: Sealing material 1: epoxy acrylate resin ("Photolec S-WF17" manufactured by Sekisui Material Solutions Co., Ltd.), not heated.

[0196] (2) Preparation of Electrochromic Sheet Example 1 An electrochromic sheet as shown in FIG. 1 was prepared by the following procedure. - Formation of First Transparent Electrode Layer - A 0.5 mm thick polycarbonate resin substrate (Polyca-Ace, deflection temperature under load: 140°C, manufactured by Sumitomo Bakelite Co., Ltd.) was prepared as a first support. An ITO film was formed on the first support by sputtering to a thickness of approximately 50 nm, and then a 5 nm thick silver alloy film was laminated thereon, followed by another 50 nm thick ITO film 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, Ltd.), 0.2 g of acetylacetone, and 0.3 g of a surfactant (polyoxyethylene octylphenyl ether, manufactured by Wako Pure Chemical Industries, Ltd.) were bead milled for 12 hours together with 5.5 g of water and 1.0 g of ethanol. To the resulting dispersion was added 1.2 g of polyethylene glycol (#20,000, manufactured by NOF Corporation) to prepare a paste. The resulting 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.

[0197] - Formation of First Electrochromic Layer - Subsequently, a 2,2,3,3-tetrafluoropropanol solution containing 1.5 mass % of a reductively color-forming 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.

[0198]

[0199] - Formation of 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 approximately 50 nm, and a silver alloy was layered thereon to a thickness of 5 nm, and another ITO film was layered thereon to a thickness of 50 nm to form a multilayer (IAI) to form a second transparent electrode layer.

[0200] - Formation of second electrochromic layer - A solution was prepared by mixing polyethylene glycol diacrylate (PEG400DA, manufactured by Nippon Kayaku Co., Ltd.), a photoinitiator (IRGACURE 184, manufactured by BASF), a radical polymerizable compound II having a triarylamine represented by the following formula as an oxidative color-developing electrochromic material, and 2-butanone in a mass ratio of 57:3:140:800 on the second transparent electrode layer. The prepared solution was then applied to an ITO glass substrate by spin coating.

[0201] (wherein Me represents a methyl group)

[0202] 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.

[0203] -Preparation of gel electrolyte- A polymerizable material (V3877, manufactured by 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, manufactured by Panac Corporation), and a solution prepared by mixing a photopolymerization initiator (Irgacure 184, manufactured by Nippon Kayaku Co., Ltd.) in an amount of 0.5 mass % relative to the polymerizable material was applied to the surface of the release-treated PET film (NP75A, manufactured by Panac Corporation). The resulting mixture was then laminated with a release-treated PET film (NP75A, manufactured by Panac Corporation) and cured with ultraviolet (UV) light to prepare a gel electrolyte.

[0204] -Laminating process- The release film was peeled off from the prepared gel electrolyte, and the gel electrolyte was laminated to the surface of the first electrochromic layer. Next, the prepared sealing material 1 was applied using a dispenser so as to surround the periphery of the side of the first electrochromic layer. After that, the second electrochromic layer of the second support and the surface of the gel electrolyte were laminated together, and the sealing material was spread to cover the side surfaces of the first and second electrochromic layers. UV light was applied at 3 J / cm. ２The 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.

[0205] 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.

[0206] 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 approximately 130 nm by a sputtering method.

[0207] 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 approximately 100 nm by a sputtering method.

[0208] (3) Measurement and Evaluation Next, the obtained electrochromic sheet was subjected to the following measurements and evaluations. The results are shown in Table 1.

[0209] [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 resulting reflected light was measured using a spectrophotometer at a viewing angle of 10°. The reflectance (%) and the CIE 1976L spectral reflectance of the reflected light were then measured. ＊ a ＊ b ＊ L in chromaticity coordinates ＊ Value a ＊ Value b ＊ Similarly, the transmittance (%) and the CIE 1976L spectral reflectance of the reflected light were measured using a spectrophotometer at a viewing angle of 10° by irradiating the surface of each electrochromic sheet facing the first support layer with light from a D65 light source at an incident angle of 90°. ＊ a ＊ b ＊ L in chromaticity coordinates ＊ Value a ＊ Value b ＊ The values ​​were calculated respectively. Spectrophotometer "V-670" manufactured by JASCO Corporation

[0210] [Deformation Amount] Using each of the obtained electrochromic sheets, a test piece (maximum length of 20 mm or more) was prepared with the electrolyte layer at the center and the sealing material at 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).

[0211] [Reflected color tint and transparency (freedom of design)] Under bright sunlight, a skilled technician picked up each electrochromic sheet obtained and looked through it. The "reflected color tint" and "transparency" of the electrochromic sheet were evaluated according to the following criteria: A: Very good. No sense of incongruity as a spectacle lens. B: Somewhat unnatural, but no problem as a spectacle lens. C: Clearly unnatural as a spectacle lens.

[0212]

[0213] This application claims priority based on Japanese Patent Application No. 2023-096391 filed on June 12, 2023, and Japanese Patent Application No. 2023-129084 filed on August 8, 2023, the disclosures of which are incorporated herein in their entireties.

[0214] REFERENCE SIGNS LIST 1 First transparent substrate 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 substrate layer 8 Sealant 10 Electrochromic element 21 Auxiliary electrode layer 22 Columnar conductive portion 30 Base lens 35 Resin layer 40 Mold 41 Upper mold 42 Lower mold 50 Protective film 61 Auxiliary electrode layer 62 Columnar conductive portion 70a Grip portion 70b Grip portion 70c Grip portion 100 Electrochromic sheet 110 Electrochromic sheet 120 Curved sheet 210 Connecting sheet laminate 220 Curved element laminate 250 Element laminate 300 Electrochromic lens

Claims

1. An electrochromic lens comprising an electrochromic element, a sealant covering the side surfaces of the electrochromic element, and a pair of transparent substrate layers sandwiching the electrochromic element and the sealant, and which satisfies the following requirement a: (Requirement a) The length of the inner peripheral edge of the sealant, measured in orthogonal projection when the sealant is viewed from the top surface of the electrochromic lens through the transparent substrate layers, is L (mm), and the area of ​​the region occupied by the sealant is S (mm ２ ), S / L is W (mm), there is a first region where W is less than 1 mm and a second region where W is 1.5 mm or more, and the area of ​​the first region is S1 (mm ２ ), and the area of ​​the second region is S2 (mm ２ ), S1 / S (percentage) is 50% or more, S2 / S (percentage) is 1 to 40%, and the second region has a length of 4 mm at any position on the inner circumferential edge of the sealing material as La, and the area of ​​the region occupied by the sealing material including La is Sa (mm ２ ) and Sa / La is Wa (mm), the region where Wa (mm) is 1.5 mm or more is included.

2. An electrochromic lens according to claim 1, wherein the electrochromic lens has a through electrode that penetrates the sealing material in the second region.

3. An electrochromic lens according to claim 1 or 2, wherein the electrochromic lens has a gripping portion in the second region.

4. An electrochromic lens according to claim 1 or 2, wherein the sealing material is formed from a resin composition containing a curable resin.

5. An electrochromic lens according to claim 1 or 2, wherein the electrochromic element is a solid or gel having a laminated structure in which an electrolyte layer and an electrochromic layer are laminated.

6. An electrochromic lens according to claim 5, wherein said electrolyte layer is a solid or a gel.

7. An electrochromic lens according to claim 1 or 2, further comprising an electrode layer between the transparent substrate layer and the electrochromic element.

8. An electrochromic lens according to claim 1 or 2, wherein the transparent substrate layer contains one or more resins selected from the group consisting of 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.

9. An electrochromic device using the electrochromic lens according to claim 1 or 2.

10. A method for using an electrochromic sheet comprising an electrochromic element, a sealant covering the side surfaces of the electrochromic element, and a pair of transparent substrate layers sandwiching the electrochromic element and the sealant, comprising a process for processing the electrochromic sheet into an electrochromic lens that satisfies the following requirement b: (requirement b) The length of the inner edge of the sealant, measured in orthogonal projection when the sealant is viewed from the top surface of the electrochromic lens through the transparent substrate layer, is L (mm), and the area of ​​the region occupied by the sealant is S (mm ２ ), S / L is W (mm), there is a first region where W is less than 1 mm and a second region where W is 1.5 mm or more, and the area of ​​the first region is S1 (mm ２ ), and the area of ​​the second region is S2 (mm ２ ), S1 / S (percentage) is 50% or more, S2 / S (percentage) is 1 to 40%, and the second region has a length of 4 mm at any position on the inner circumferential edge of the sealing material as La, and the area of ​​the region occupied by the sealing material including La is Sa (mm ２ ) and Sa / La is Wa (mm), the region where Wa (mm) is 1.5 mm or more is included.

11. An electrochromic sheet comprising a support layer, an electrolyte layer provided on the support layer, an electrochromic layer provided on at least one surface of the electrolyte layer, and a pair of transparent electrode layers located on the support layer so as to sandwich the electrolyte layer and the electrochromic layer, the electrochromic sheet being configured to satisfy the following condition 1. (Condition 1) When the surface of the electrochromic sheet facing the support layer of the electrochromic sheet 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 standard deviation of the reflected light is 1.25°. ＊ a ＊ b ＊ a in chromaticity coordinates ＊ is -15 to 15, b ＊ is between -20 and 10.

12. The electrochromic sheet according to claim 11, further configured to satisfy the following condition 2: (Condition 2) When 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 of the reflected light is ＊ a ＊ b ＊ L in chromaticity coordinates ＊ is between 20 and 50.

13. An electrochromic sheet according to claim 11 or 12, further configured to satisfy the following condition 3: (Condition 3) When 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 transmitted light is measured with a spectrophotometer at a viewing angle of 10°, the transmittance is 70 to 99%.

14. An electrochromic sheet according to claim 11 or 12, further comprising a sealant on the support layer that covers the electrolyte layer and the side surfaces of the electrochromic layer, and 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 sealant 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 taken as the deformation amount (mm). The deformation amount is 0.01 mm to 0.09 mm.

15. The electrochromic sheet according to claim 11 or 12, wherein the transparent electrode layer has a thickness of 40 to 200 nm.

16. The electrochromic sheet according to claim 11 or 12, wherein at least one of the pair of transparent electrode layers has a multi-layer structure.

17. An electrochromic sheet according to claim 11 or 12, 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.

18. The electrochromic sheet according to claim 11 or 12, wherein the transparent electrode layer has a single-layer or multi-layer structure comprising a layer 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), a silver alloy, and polypyrrole, polyaniline, polythiophene, poly(p-phenylene), polyfluorene, and derivatives thereof.

19. The electrochromic sheet according to claim 11 or 12, wherein the pair of transparent electrode layers are made of different materials.

20. The electrochromic sheet according to claim 11 or 12, wherein the pair of transparent electrode layers are made of the same material.

21. An electrochromic sheet according to claim 11 or 12, wherein the support layer contains one or more resins selected from the group consisting of 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.

22. An electrochromic device using the electrochromic sheet according to claim 11 or 12.

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