Electrochromic sheet, laminate, eyeglass lens, eyeglasses

Abstract

To provide an electrochromic sheet capable of developing and decoloring color without delay. [Solution] An electrochromic sheet comprising a first substrate, a second substrate, an electrochromic element sandwiched between the first and second substrates, and a sealing portion sandwiched between the first and second substrates and defining a colored region set between the first and second substrates, wherein the first substrate has a first resin substrate and a first thermal expansion suppression layer provided on the first resin substrate, and the electrochromic element has a first transparent electrode provided on the first thermal expansion suppression layer side of the first substrate, a first auxiliary electrode arranged around the colored region, electrically connected to the first transparent electrode and including a sintered body of metal particles, a second transparent electrode provided on the second substrate side, and an electrochromic layer sandwiched between the first transparent electrode and the second transparent electrode, arranged in the colored region, and which becomes colored by the application of a voltage.

Description

[Technical Field]

[0001] The present invention relates to an electrochromic sheet, a laminate, a lens for glasses, and glasses. [Background technology]

[0002] Electrochromism is a phenomenon in which an applied voltage causes a redox reaction, resulting in a reversible color change. Electrochromic elements, which utilize this phenomenon and control the color by applying a voltage using electrochromic materials, are known.

[0003] An electrochromic element includes, for example, an electrochromic layer that develops or loses color when a voltage is applied, and transparent electrodes that sandwich the electrochromic layer and are electrically connected to the electrochromic layer (see, for example, Patent Document 1).

[0004] Electrochromic sheets equipped with electrochromic elements are used, for example, as materials for eyewear such as sunglasses and wearable devices such as smart glasses. They are also used as light-adjusting components (optical filters) in windows and imaging devices. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-167317 Summary of the Invention [Problem to be solved by the invention]

[0006] The transparent electrodes used in the configuration of Patent Document 1 are formed using a material having high electrical conductivity and high visible light transmittance. Known materials for transparent electrodes include oxides such as ITO (Indium Tin Oxide).

[0007] However, the above materials have higher electrical resistance than metal materials, so in an electrochromic layer sandwiched between transparent ITO electrodes, there are areas where current easily flows and areas where it does not, which can easily cause uneven color changes (coloring and decoloring) in the electrochromic layer.

[0008] The present invention has been made in view of the above circumstances, and aims to provide an electrochromic sheet that can develop and decolor without delay. It is also an object of the present invention to provide a laminate including such an electrochromic sheet, an eyeglass lens, and eyeglasses including the eyeglass lens. [Means for solving the problem]

[0009] To solve the above problems, the inventors have investigated a configuration in which an auxiliary electrode is used in combination with a transparent electrode to compensate for the conductivity of the transparent electrode. Generally, an auxiliary electrode is formed using a metal material having a lower electrical resistance than the material of the transparent electrode. During the investigation, the inventors discovered that when a resin substrate, which is more susceptible to thermal expansion than glass, is used as the substrate, the substrate thermally expands during the heating and baking process for forming the auxiliary electrode, which makes it more likely that film peeling or cracks will occur in the auxiliary electrode. In other words, the inventors discovered that there are cases in which the auxiliary electrode is unable to fully perform its expected function. Based on this finding, the inventors have conducted extensive research and completed the present invention.

[0010] In order to solve the above problems, one aspect of the present invention includes the following aspects.

[0011] [1] An electrochromic sheet comprising: a first substrate, a second substrate, an electrochromic element sandwiched between the first substrate and the second substrate; and a sealing portion sandwiched between the first substrate and the second substrate and defining a colored region set between the first substrate and the second substrate, wherein the first substrate has a first resin substrate and a first thermal expansion suppression layer provided on the first resin substrate, and the electrochromic element has: a first transparent electrode provided on the first thermal expansion suppression layer side of the first substrate; a first auxiliary electrode arranged around the colored region, electrically connected to the first transparent electrode and including a sintered body of metal particles; a second transparent electrode provided on the second substrate side; and an electrochromic layer sandwiched between the first transparent electrode and the second transparent electrode, arranged in the colored region, and colored by application of a voltage.

[0012] [2] The electrochromic sheet according to [1], wherein the second substrate further comprises a second resin substrate and a second thermal expansion suppression layer provided on the second resin substrate, and the electrochromic element further comprises a second auxiliary electrode disposed around the colored region, electrically connected to the second transparent electrode, and including the sintered body.

[0013] [3] The electrochromic sheet according to [2], further comprising either or both of a first electrode protective layer and a second electrode protective layer, wherein the first electrode protective layer is in contact with the first auxiliary electrode, the first auxiliary electrode being sandwiched between the first transparent electrode and the first electrode protective layer, and the second electrode protective layer is in contact with the second auxiliary electrode, and the second auxiliary electrode being sandwiched between the second transparent electrode and the second electrode protective layer.

[0014] [4] The electrochromic sheet according to [2] or [3], wherein the first auxiliary electrode has a first opposing electrode portion extending along a part of the outer periphery of the colored region, the second auxiliary electrode has a second opposing electrode portion extending along another part of the outer periphery of the colored region, the second opposing electrode portion is on the opposite side of the colored region from the first opposing electrode portion and faces the first opposing electrode portion, and the width of the portion including at least one end of the first opposing electrode portion and the second opposing electrode portion is 0.1 mm or more and 2.0 mm or less.

[0015] [5] The electrochromic sheet according to [4], wherein the average thickness of the first auxiliary electrode and the second auxiliary electrode is 4 μm or less in a cross section of the first opposing electrode portion and the second opposing electrode portion, the cross section being 150 μm wide from the end of the colored region side in the short direction.

[0016] [6] The electrochromic sheet according to any one of [2] to [5], wherein one or both of the first thermal expansion suppression layer and the second thermal expansion suppression layer is made of a curable resin containing a filler.

[0017] [7] The electrochromic sheet according to any one of [2] to [6], wherein either or both of the first auxiliary electrode and the second auxiliary electrode further contain an organic π-conjugated ligand.

[0018] [8] The electrochromic sheet according to any one of [2] to [7], wherein either or both of the first auxiliary electrode and the second auxiliary electrode have a gap.

[0019] [9] The electrochromic sheet according to any one of [2] to [8], wherein either one or both of the first resin substrate and the second resin substrate comprises a thermoplastic resin, and the glass transition temperature of the thermoplastic resin is 200°C or lower.

[0020]

[10] The electrochromic sheet according to any one of [2] to [9], wherein the first auxiliary electrode and the second auxiliary electrode are electrically connected to terminals for applying voltage independently in a cross section of the first auxiliary electrode and the second auxiliary electrode in the thickness direction.

[0021]

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

[10] , wherein either or both of the first transparent electrode and the second transparent electrode contain indium oxide.

[0022]

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

[11] , which has been plastically deformed.

[0023]

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

[12] , and a lens material on which the electrochromic sheet is laminated.

[0024]

[14] An electrochromic section obtained by cutting the electrochromic sheet according to any one of [2] to

[10] along the outer peripheries of the first auxiliary electrode and the second auxiliary electrode; and a lens body on which the electrochromic portion is laminated.

[0025]

[15] Eyeglasses comprising the eyeglass lens according to

[14] and a frame that holds the eyeglass lens, wherein the lens body is electrically connected to the frame. [Effects of the Invention]

[0026] According to the present invention, it is possible to provide an electrochromic sheet capable of coloring and decoloring without delay, and also to provide a laminate including such an electrochromic sheet, an eyeglass lens, and eyeglasses including the eyeglass lens. [Brief explanation of the drawings]

[0027] [Figure 1]FIG. 1 is a perspective view showing sunglasses (eyeglasses) using the electrochromic sheet of the embodiment as a material. [Figure 2] FIG. 2 is an exploded perspective view showing an example of the electrochromic sheet 150. As shown in FIG. [Figure 3] Fig. 3(a) is a diagram showing an example of a partial cross section taken along line III-III in Fig. 2 (in the diagram, the arrow indicates that the contact portion between the conductive portion 52 and the terminal for applying voltage is on the upper surface of the sheet). Fig. 3(b) is a diagram showing an example of a partial cross section taken along line III-III when the electrochromic sheet 150 is processed into a lens 110 (in the diagram, the arrow indicates that the contact portion between the conductive portion 52 and the terminal for applying voltage is on the side surface of the lens). [Figure 4] FIG. 4 is a plan view showing an example of the EC sheet 150. As shown in FIG. [Figure 5] FIG. 5 is an explanatory diagram illustrating a method for manufacturing a lens using the EC sheet 150. [Figure 6] Fig. 6(a) is a Nyquist diagram (display range of Z': 0Ω to 100Ω) created for the EC sheet of Example 1. Fig. 6(b) is a Nyquist diagram (display range of Z': 0Ω to 50000Ω) created for the EC sheet of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0028] The electrochromic sheet, laminate, eyeglass lens, and eyeglasses according to the present embodiment will be described below with reference to Figures 1 to 6. In all of the following drawings, the dimensions and proportions of each component have been appropriately changed to make the drawings easier to understand. In the following description, the term "electrochromic" may be abbreviated as "EC."

[0029] ≪Glasses≫ 1 is a perspective view showing sunglasses (eyeglasses) made from the electrochromic sheet (EC sheet) of this embodiment. Sunglasses are an example of eyeglasses.

[0030] In this specification, the term "eyeglasses" refers to any device (eyewear in general) worn on the user's head with lenses positioned in front of the user's eyes. In this definition, "eyeglasses" includes not only regular eyeglasses that correct the user's vision, but also well-known eyewear such as sunglasses and goggles that protect the user's eyes, and smart glasses (wearable devices) that display information on the lenses.

[0031] As shown in FIG. 1, sunglasses 100 include a pair of lenses 110 (eyeglass lenses) and a frame 120 that holds the lenses 100.

[0032] [lens] Lens 110 is transparent to visible light and can reversibly develop or fade color by switching the voltage applied. In this specification, the term "lens (eyeglass lens)" includes both lenses with and without a light-condensing function.

[0033] The lens 110 has an electrochromic portion 111 (EC portion 111) formed from an EC sheet described below, and a lens body 115 on which the EC portion 111 is laminated. When a user wears the sunglasses 100, the lens body 115 is located on the user side, and the EC portion 111 is located on the side of the lens body 115 opposite the user. The EC portion 111 may also be located on the side of the lens body 115 facing the user.

[0034] Frame The frame 120 includes a pair of rim portions 121, a bridge portion 122, a pair of temple portions 123, and a pair of nose pad portions 124. The frame 120 is worn on the head of a user. The frame 120 positions the lenses 110 in front of the eyes of the user.

[0035] The rim portions 121 are formed in a closed ring shape. The pair of rim portions 121 correspond to the right and left eyes of the user, respectively. The rim portions 121 may be in an open ring shape. Furthermore, the frame 120 may not have the rim portions 121.

[0036] The bridge portion 122 connects the pair of rim portions 121. When worn on the user's head, the bridge portion 122 is located in front of the top of the user's nose.

[0037] The pair of temple portions 123 are connected to the rim portion 121 at positions opposite to the position where the bridge portion 122 is connected. The temple portions 123 are hooked over the user's ears when the glasses are worn on the user's head.

[0038] The temple portion 123 has a switch 125 and a battery 126. The switch 125 is exposed on the outer surface of the temple portion 123. The switch 125 is electrically connected to the lens 110 via a wire. The switch 125 can switch between applying a positive voltage, applying a negative voltage, and not applying a voltage to the lens 110, for example.

[0039] The battery 126 is built into the temple portion 123. The battery 126 is electrically connected to the lens 110 via a wire.

[0040] The nose pads 124 are formed on each rim 121 at positions corresponding to the nose of the user. The nose pads 124 come into contact with the nose of the user. The nose pads 124 stabilize the wearing state of the sunglasses 100.

[0041] For example, metal materials, resin materials, etc. can be used as the constituent material of the frame 120. The shape of the frame 120 is not limited to the example shown in the figure, as long as it is a shape that can be worn on the user's head.

[0042] <Electrochromic Sheet> Fig. 2 is an exploded perspective view showing an example of an electrochromic sheet 150. Fig. 3 is a diagram showing an example of a partial cross-sectional view taken along line III-III in Fig. 2. The EC sheet 150 is used as a material for eyeglass lenses, which will be described later.

[0043] 2 and 3, the EC sheet 150 includes a first substrate 21, a second substrate 22, an electrochromic element 30 (EC element 30), and a sealing portion 40. In Fig. 2, the sealing portion 40 is omitted.

[0044] The first substrate 21 and the second substrate 22 sandwich the EC element 30 and the sealing portion 40. The sealing portion 40 is disposed around the EC element 30 between the first substrate 21 and the second substrate 22, and separates the first substrate 21 and the second substrate 22. The region of the EC element 30 separated by the sealing portion 40 is a colored region AR whose color changes when a voltage is applied.

[0045] [First board, second board] The first substrate 21 and the second substrate 22 are the outermost layers of the EC sheet 150. The first substrate 21 and the second substrate 22 are arranged opposite to each other, and hold the EC element 30 and the like, and also function as a protective layer that protects the EC element 30 and the like.

[0046] The first substrate 21 and the second substrate 22 are visible light transmissive. In this specification, having visible light transmissive property may be referred to as "transparency." Visible light transmissive property may also be referred to as "transparency." If they are transparent, the first substrate 21 and the second substrate 22 may be colorless or colored.

[0047] The first substrate 21 has a first resin substrate 23 and a first thermal expansion suppressing layer 24 provided on the first resin substrate. When the electrochromic element described below has a second auxiliary electrode, the second substrate 22 preferably has a second resin substrate 26 and a second thermal expansion suppressing layer 25 provided on the second resin substrate.

[0048] In this specification, the term "provided on a resin substrate" means that a first thermal expansion suppressing layer is formed on a first resin substrate directly or via another layer, or a second thermal expansion suppressing layer is formed on a second resin substrate directly or via another layer. The other layer is not particularly limited as long as it is transparent, and examples thereof include an adhesion layer, a water vapor barrier layer, a gas barrier layer, and an optical adjustment layer.

[0049] (First resin substrate, second resin substrate) The first resin substrate 23 and the second resin substrate 26 contain a transparent thermoplastic resin as a main material. Examples of such resins include acrylic resins, polystyrene resins, polyethylene resins, polypropylene resins, polyester resins (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), polycarbonate resins, polyamide resins, cycloolefin resins, vinyl chloride resins, polyacetal resins, and triacetyl cellulose (TAC). The first resin substrate 23 and the second resin substrate 26 may be made of one of the above resins, or may be made of a combination of two or more of them.

[0050] In particular, it is preferable that either or both of the first resin substrate 23 and the second resin substrate 26 contain a thermoplastic resin having a glass transition temperature of 200° C. or lower, and it is more preferable that both of the first resin substrate 23 and the second resin substrate 26 contain a thermoplastic resin having a glass transition temperature of 200° C. or lower. The upper limit of the glass transition temperature is more preferably 180° C. or lower, and even more preferably 160° C. or lower. When the glass transition temperature is equal to or lower than the upper limit, the thermal processability of the resin substrate is superior. The lower limit of the glass transition temperature is not particularly limited, but is sufficient as long as it is 80° C. or higher, preferably 100° C. or higher, and more preferably 120° C. or higher. When the glass transition temperature is equal to or higher than the above lower limit, the heat resistance of the resin substrate becomes more excellent. The above upper and lower limit values ​​can be arbitrarily combined for the glass transition temperatures of the first resin substrate 23 and the second resin substrate 26. The thermoplastic resin having a glass transition temperature equal to or lower than the above temperature is preferably a polycarbonate-based resin, a polyester-based resin, or a polyamide-based resin.

[0051] The first resin substrate 23 and the second resin substrate 26 may contain known fillers and additives as long as they are transparent.

[0052] The first resin substrate 23 and the second resin substrate 26 may each be a single layer, or may be laminated in two or three layers.

[0053] The average thickness of the first resin substrate 23 and the second resin substrate 26 is, for example, 0.05 mm or more and 10.0 mm or less, and preferably 0.1 mm or more and 5.0 mm or less.

[0054] (First thermal expansion suppression layer, second thermal expansion suppression layer) The first thermal expansion suppressing layer 24 is provided on the first resin substrate 23. The first thermal expansion suppressing layer 24 is less susceptible to thermal expansion than the first resin substrate 23. Therefore, deformation of the first auxiliary electrode 33 due to thermal expansion of the resin substrate 23 is suppressed when the auxiliary electrode (first auxiliary electrode 33 or second auxiliary electrode 34) is heated and baked or when the EC sheet is heated and bent, and peeling and cracking of the first auxiliary electrode 33 are less likely to occur.

[0055] The second thermal expansion suppressing layer 25 is provided on the second resin substrate 26. The second thermal expansion suppressing layer 25 is less susceptible to thermal expansion than the second resin substrate 26. Therefore, deformation of the second auxiliary electrode 34 due to thermal expansion of the second resin substrate 26 is suppressed when the auxiliary electrode is heated and baked or when the EC sheet is heated and bent, and peeling and cracking of the second auxiliary electrode 34 are less likely to occur.

[0056] The first thermal expansion suppression layer 24 and the second thermal expansion suppression layer 25 contain a transparent thermosetting resin or photocurable resin as a main material. Such curable resins are not particularly limited as long as they can suppress the thermal expansion of the first resin substrate 23 and the second resin substrate 26, respectively, but examples include acrylic resin, urethane resin, and epoxy resin. Resin materials with a cured resin having a higher glass transition temperature than the resin substrates on which the thermal expansion suppression layers are formed are particularly preferred. The high glass transition temperature of the cured resin effectively suppresses deformation of the auxiliary electrodes due to thermal expansion of the resin substrates during heating and baking of the auxiliary electrodes or heating and bending of the EC sheet. The first thermal expansion suppressing layer 24 and the second thermal expansion suppressing layer 25 may be made of one of the above resins, or a combination of two or more of them.

[0057] The content of the curable resin in the thermal expansion suppressing layer 12 is not particularly limited, but may be 20% by mass or more and 99.9% by mass or less, and preferably 30% by mass or more and 90% by mass or less, based on the total amount of the thermal expansion suppressing layer 12.

[0058] In particular, it is preferable that either or both of the first thermal expansion suppression layer 24 and the second thermal expansion suppression layer 25 be made of a curable resin containing a filler, and it is even more preferable that both the first thermal expansion suppression layer 24 and the second thermal expansion suppression layer 25 be made of a curable resin containing a filler. The filler is not particularly limited as long as it is transparent. The filler material may have a smaller linear thermal expansion coefficient than the resin substrate on which the thermal expansion suppression layer is formed, and inorganic materials (oxides, nitrides, metals, etc.) are preferably selected. This is because inorganic materials have a smaller linear thermal expansion coefficient than organic resin substrates. Specific examples of inorganic filler materials include silicon oxide, zirconia oxide, aluminum oxide, tin oxide, aluminum nitride, aluminum boride, various micas, Ag, Cu, Au, Ni, and carbon. The filler material may also have a core-shell structure composed of multiple materials. The filler material may be surface-treated with hydroxyl groups, acrylic groups, epoxy groups, etc. to suppress filler aggregation or improve mixability with the resin. The filler may be in the form of a sphere, fiber, flake, hollow particle, etc. The particle size of the filler may be from 2 nm to 500 μm, preferably from 10 nm to 10 μm. Fillers of different shapes or particle sizes may be mixed and used.

[0059] The filler content in the first thermal expansion suppressing layer 24 and the second thermal expansion suppressing layer 25 may be 1% by mass or more, and preferably 10% by mass or more and 200% by mass or less, based on the total amount of the curable resin. By adjusting the filler content within the above numerical range, the ease of thermal expansion of the first thermal expansion suppressing layer 24 and the second thermal expansion suppressing layer 25 can be adjusted without impairing the effects of the present invention. For example, by increasing the filler content, the first thermal expansion suppressing layer 24 and the second thermal expansion suppressing layer 25 can be made less susceptible to thermal expansion. Furthermore, by reducing the filler content, the film quality of the first thermal expansion suppressing layer 24 and the second thermal expansion suppressing layer 25 can be further improved, and film defects can be further reduced.

[0060] As long as the material of the first thermal expansion suppressing layer 24 and the second thermal expansion suppressing layer 25 is transparent, it may contain known additives.

[0061] The first thermal expansion suppressing layer 24 and the second thermal expansion suppressing layer 25 may each be a single layer, or may be a laminate of two or three layers.

[0062] The average thickness of the first thermal expansion suppressing layer 24 and the second thermal expansion suppressing layer 25 is, for example, preferably 0.1 μm to 500 μm, more preferably 0.5 μm to 50 μm, and even more preferably 1 μm to 10 μm. When the average thickness of the first thermal expansion suppressing layer 24 and the second thermal expansion suppressing layer 25 is within the above numerical range, peeling or cracking of the sintered body is less likely to occur during heating and firing of the auxiliary electrode or during heating and bending of the EC sheet. Furthermore, when the average thickness of the first thermal expansion suppressing layer 24 and the second thermal expansion suppressing layer 25 is less than the above upper limit, peeling or cracking of the thermal expansion suppressing layer itself is less likely to occur during bending.

[0063] The refractive index of the first substrate 21 and the second substrate 22 at a wavelength of 589 nm 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 of the first substrate 21 and the second substrate 22 to this range, the function of the electrochromic element 30 can be improved.

[0064] By providing a thermal expansion suppression layer on the substrate, the electrochromic sheet of this embodiment is less likely to peel or crack when sintered, even when using a resin substrate that is more susceptible to thermal expansion than glass. Therefore, in the electrochromic sheet of this embodiment, the auxiliary electrode is less likely to have high electrical resistance. This means that the range of materials that can be used for the resin substrate can be expanded, and thermoplastic resins that are easy to process during the heating and firing of the auxiliary electrode and the heating and bending of the EC sheet can be used for the resin substrate.

[0065] [Electrochromic element] The EC element 30 changes color (coloring or decoloring) due to electrochromism caused by application of a voltage. The EC element 30 has a first transparent electrode 31, a first auxiliary electrode 33, a second transparent electrode 32, and an electrochromic layer 35 (EC layer 35). The EC element 30 preferably has a second auxiliary electrode 34, and more preferably further has either or both of a first electrode protective layer 36 and a second electrode protective layer 37.

[0066] (1st transparent electrode, 2nd transparent electrode) The first transparent electrode 31 is provided on the first thermal expansion suppression layer 24 side of the first substrate 21 of the EC element 30, and is formed on the surface of the first substrate 21 facing the second substrate 22. The second transparent electrode 32 is provided on the second substrate 22 side of the EC element 30, and is formed on the surface of the second substrate 22 facing the first substrate 21.

[0067] 2, the first transparent electrode 31 has a protruding portion 31a at a position overlapping a first extraction portion 332 (described later) similar to the first extraction portion 332, but this portion 31a may be absent. Similarly, the second transparent electrode 32 has a protruding portion 32a at a position overlapping a second extraction portion 342 (described later) similar to the second extraction portion 342, but this portion 32a may be absent.

[0068] The first transparent electrode 31 and the second transparent electrode 32 are transparent. Examples of materials for the first transparent electrode 31 and the second transparent electrode 32 include oxides such as ITO, FTO (F-doped tin oxide), ATO (antimony tin oxide), IZO (indium zinc oxide), In2O3, SnO2, and Al-containing ZnO, Au, Pt, Ag, Cu, or alloys containing these, carbon, and conductive polymers. The first transparent electrode 31 and the second transparent electrode 32 may be made of one of these materials, or two or more of these materials may be used in combination. Metallic materials with low transparency can be used as transparent electrodes by thinning them or forming them into a lattice shape to increase the voids. In particular, it is preferable that either one or both of the first transparent electrode 31 and the second transparent electrode 32 contain indium oxide, as this results in better density and transparency of the first transparent electrode 31 and the second transparent electrode 32. The inclusion of indium oxide makes it easier to protect the EC layer 35 from oxygen and water. More specifically, the auxiliary electrode containing indium oxide more preferably contains ITO, IZO, ITO, or In2O3, and even more preferably contains ITO. The first transparent electrode 31 and the second transparent electrode 32 may be made of the same material or different materials.

[0069] The thickness of the first transparent electrode 31 and the second transparent electrode 32 is adjusted so as to ensure the necessary transparency and to obtain an electrical resistance value that allows an appropriate current to flow through the EC layer 35. When ITO is used as the material for the first transparent electrode 31 and the second transparent electrode 32, the average thickness of the first transparent electrode 31 and the second transparent electrode 32 is, for example, independently set to 50 nm or more and 200 nm or less, preferably 50 nm or more and 150 nm or less, and more preferably 60 nm or more and 130 nm or less. The first transparent electrode 31 and the second transparent electrode 32 may be formed to have the same average thickness or may be formed to have different thicknesses. Furthermore, since the first transparent electrode 31 and the second transparent electrode 32 are electrically connected to the first auxiliary electrode 31 and the second auxiliary electrode 32 arranged around the colored area AR, they are formed larger than the colored area AR and are formed to extend to the formation area of ​​the sealing portion 40 or part of the formation area.

[0070] (1st auxiliary electrode, 2nd auxiliary electrode) First auxiliary electrode 33 is disposed around colored region AR in the peripheral portion of first transparent electrode 31, is electrically connected to first transparent electrode 31, and includes a sintered body of metal particles.

[0071] The first auxiliary electrode 33 includes a first opposing electrode portion 331 and a first extraction portion 332. The first opposing electrode portion 331 extends along part of the outer periphery of the colored region AR. The first opposing electrode portion 331 is formed away from the outer periphery of the colored region AR. The first extraction portion 332 protrudes from the first opposing electrode portion 331 to the outside of the colored region AR.

[0072] The first opposing electrode portion 331 surrounds a portion of the EC layer 35, i.e., a portion of the colored region AR. The first opposing electrode portion 331 is curved in a plan view, but is not limited to this. When the first opposing electrode portion 331 is formed as a lens 110, the first opposing electrode portion 331 is provided in a position that surrounds the periphery of the lens 110. The width of the first opposing electrode portion 331 is preferably, for example, 0.1 mm to 2.0 mm, and more preferably 0.3 mm to 1.0 mm.

[0073] The first extraction portion 332 is provided at one end of the first opposing electrode portion 331. When the lens 110 is formed, the first extraction portion 332 is provided at a position in the frame 120 near the bridge portion 122 or the temple portion 123.

[0074] When the EC element 30 has the second auxiliary electrode 34, the first auxiliary electrode 33 and the second auxiliary electrode 34 are spaced apart in the circumferential direction of the colored region AR and are arranged around the colored region AR, so that the first auxiliary electrode 33 and the second auxiliary electrode 34 surround the colored region AR.

[0075] The second auxiliary electrode 34 includes a second opposing electrode portion 341 and a second extraction portion 342. The second opposing electrode portion 341 extends along a portion of the outer periphery of the colored region AR. The second opposing electrode portion 341 is located on the opposite side of the colored region AR from the first opposing electrode portion 331 and faces the first opposing electrode portion 331. The second opposing electrode portion 341 is formed away from the outer periphery of the colored region AR. The second extraction portion 342 protrudes from the second opposing electrode portion 341 to the outside of the colored region AR.

[0076] The second opposing electrode portion 341 surrounds a portion of the EC layer 35, i.e., a portion of the colored region AR. The second opposing electrode portion 341 is curved in a plan view, but is not limited to this. When the second opposing electrode portion 341 is formed as a lens 110, the second opposing electrode portion 341 is provided in a position that surrounds the periphery of the lens 110. The width of a portion of the second opposing electrode portion 341 that includes at least one end is preferably, for example, 0.1 mm to 2.0 mm, and more preferably 0.3 mm to 1.0 mm.

[0077] The second output portion 342 is provided at one end of the second opposing electrode portion 341. When the lens 110 is formed, the second output portion 342 is provided at a position in the frame 120 near the bridge portion 122 or the temple portion 123.

[0078] The positions of the first extraction section 332 and the second extraction section 342 can be adjusted as appropriate depending on the design of the lens 110 to be manufactured.

[0079] Furthermore, the first auxiliary electrode 33 is electrically connected to a terminal for applying a voltage in a cross section of the first auxiliary electrode 33 in the thickness direction.

[0080] 3(a), when the EC sheet 150 is processed into the lens 110, a through-hole 40a exposing the first extraction portion 332 is formed in the sealing portion 40 at a position overlapping the first extraction portion 332 in plan view, and a conductive portion 51 is formed in the through-hole 40a. The first extraction portion 332 is used as a connection point with the conductive portion 51. The formed conductive portion 51 is electrically connected to the first extraction portion 332 (first auxiliary electrode 33).

[0081] Furthermore, the second auxiliary electrode 34 is also electrically connected to a terminal for applying a voltage in a cross section in the thickness direction of the second auxiliary electrode. More specifically, a through hole 40b exposing the second extraction portion 342 is similarly formed in the sealing portion 40 at a position overlapping the second extraction portion 342 in plan view, and a conductive portion 52 is formed in the through hole 40b. The second extraction portion 342 is used as a connection point with the conductive portion 52. The formed conductive portion 52 is electrically connected to the second extraction portion 342 (second auxiliary electrode 34).

[0082] 3(b), from the viewpoint of making the colored area AR larger, after the EC sheet 150 is processed into the lens 110, the conductive portions 51 and 52 may be formed on the side surfaces of the lens 110. The formed conductive portions 51 and 52 are electrically connected to the first auxiliary electrode 33 and the second auxiliary electrode 34, respectively.

[0083] Although the connection portion between the conductive portion 52 and the second auxiliary electrode 34 shown in FIG. 3(b) is illustrated as a straight line and has a substantially flat surface, the connection portion between the conductive portion 52 and the second auxiliary electrode 34 may have an uneven shape. That is, the connection portion may be formed by the uneven shape formed on the conductive portion 52 engaging with the uneven shape formed on the second auxiliary electrode 34. This ensures a large contact area between the conductive portion 52 and the second auxiliary electrode 34 at the connection portion. As a result, the connection resistance of the connection portion can be reduced. Furthermore, in addition to the connection portion between the conductive portion 52 and the second auxiliary electrode 34, the connection portion between the conductive portion 52 and the second transparent electrode 32 and the connection portion between the conductive portion 52 and the sealing portion 40 may also have an uneven shape. This reduces the connection resistance of the connection portion and further increases the mechanical connection strength.

[0084] Similar to the connection between the conductive portion 52 and the second auxiliary electrode 34, the connection between the conductive portion 51 and the first auxiliary electrode 33 may have an uneven shape. That is, the connection may be formed by the uneven shape formed on the conductive portion 51 engaging with the uneven shape formed on the first auxiliary electrode 33. This ensures a wide contact area between the conductive portion 51 and the first auxiliary electrode 33 at the connection. As a result, the connection resistance of the connection can be reduced. Furthermore, in addition to the connection between the conductive portion 51 and the first auxiliary electrode 33, the connection between the conductive portion 51 and the first transparent electrode 31 and the connection between the conductive portion 51 and the sealing portion 40 also have an uneven shape. This reduces the connection resistance of the connection and further increases the mechanical connection strength.

[0085] At the connection portion between the conductive portion 52 and the second auxiliary electrode 34, the second transparent electrode 32, or the sealing portion 40, the uneven shape may be set only at the connection portion with the second auxiliary electrode 34, or the uneven shape may be set at least at the connection portion with the second auxiliary electrode 34, or the uneven shape may be set in all layers.

[0086] Furthermore, when an uneven shape is set in all layers, the mechanical connection strength between the conductive portion 52 and each layer can be particularly increased, and the processing efficiency of the uneven shape can be further improved. Specifically, a process sequence can be adopted in which, after all layers are stacked, grooves are formed on the side surfaces of the laminate, and then the conductive portion 52 is formed so as to fill the grooves. This allows the uneven shape to be processed more efficiently.

[0087] Similarly, at the connection portion between the conductive portion 51 and the first auxiliary electrode 33, the first transparent electrode 31, or the sealing portion 40, the uneven shape may be set only at the connection portion with the first auxiliary electrode 33, or the uneven shape may be set at least at the connection portion with the first auxiliary electrode 33, or the uneven shape may be set in all layers.

[0088] Furthermore, when an uneven shape is set in all layers, the mechanical connection strength between the conductive portion 51 and each layer can be particularly increased, and the processing efficiency of the uneven shape can be further improved. Specifically, a process sequence can be adopted in which, after all layers are stacked, grooves are formed on the side surfaces of the laminate, and then the conductive portion 51 is formed so as to fill the grooves. This allows the uneven shape to be processed more efficiently.

[0089] The electrical resistance of the first auxiliary electrode 33 is lower than the electrical resistance of the first transparent electrode 31. Similarly, the electrical resistance of the second auxiliary electrode 34 is lower than the electrical resistance of the second transparent electrode 32. The first auxiliary electrode 33 and the second auxiliary electrode 34 may contain a sintered body of metal particles. Examples of metal particles include particles of gold, silver, copper, aluminum, platinum, palladium, nickel, and tungsten. As the metal particles, one of these may be used, or two or more of these may be used in combination. Among these, silver particles or copper particles are preferred as the metal particles.

[0090] In order to further increase the efficiency of light sintering, the metal particles may contain a light absorbing material, such as indium oxide, tungsten oxide, or LaB6, which are infrared absorbing particles. The size of the metal particles is preferably an average particle diameter of 2 nm to 500 nm, more preferably 2 nm to 100 nm. By having the size of the metal particles within the above numerical range, sintering can be performed at a lower temperature. Note that particles of different sizes may be mixed and used as the metal particles.

[0091] In this specification, unless otherwise specified, the term "average particle size" refers to the particle size at 50% accumulation of particles (D50) when the particle size distribution of particles is measured on a volume basis by a laser diffraction particle size distribution measurement method.

[0092] The first auxiliary electrode 33 and the second auxiliary electrode 34 can be formed, for example, by printing with ink containing metal particles. Specifically, they can be formed by discharging and coating droplets of ink containing metal nanoparticles, and then sintering the metal particles.

[0093] As a coating method, inkjet or screen printing is preferred from the viewpoint of superior patterning precision.

[0094] The sintering method is not particularly limited as long as it can produce a sintered body of metal particles, and examples thereof include local heating methods such as plasma treatment, dielectric heating treatment, excimer light irradiation treatment, flash lamp light irradiation treatment, ultraviolet treatment, microwave treatment, infrared heater treatment, and hot air heater treatment. Among these, it is preferable to sinter the metal particles by irradiating them with a laser. When irradiating the metal particles with a laser, it is possible to selectively heat only the metal particles by selecting a laser wavelength that is not absorbed by the resin substrate. Therefore, it is possible to further suppress thermal deformation of the resin substrate. Specifically, the wavelength of the laser is preferably an infrared wavelength or a visible light wavelength.

[0095] The electrochromic sheet of this embodiment has a thermal expansion suppression layer on the resin substrate, which suppresses deformation of the auxiliary electrode even when heated and fired at temperatures that tend to thermally expand the resin substrate, making it less likely to peel or crack. Furthermore, even during thermal processing of the electrochromic sheet, deformation of the auxiliary electrode due to thermal expansion of the resin substrate is suppressed, making it less likely to peel or crack. These factors result in an auxiliary electrode that is less likely to have high electrical resistance.

[0096] Preferably, either or both of the first auxiliary electrode 33 and the second auxiliary electrode 34 further contain an organic π-conjugated ligand, and more preferably, both of the first auxiliary electrode 33 and the second auxiliary electrode 34 further contain an organic π-conjugated ligand. By including the organic π-conjugated ligand, the organic π-conjugated ligand forms a π-bond with the metal particle, resulting in high conductivity due to the strong π-bond and the close proximity between the particles. Here, the π-bond refers to the parallel bonding of the π-conjugated plane of the π-conjugated molecule to the surface of the metal particle, and is a strong interaction between the organic π-orbital and the metal particle orbital that occurs when the organic π-orbital is close to the metal particle surface. Furthermore, the organic π-conjugated ligand is an organic ligand that acts on the metal particle through such a π-bond.

[0097] The organic π-conjugated ligand preferably has at least one substituent selected from the group consisting of an amino group, a mercapto group, a hydroxy group, a carboxy group, a phosphine group, a phosphonic acid group, a halogen group, a cenol group, a sulfide group, and a selenoether group, which is coordinated to the surface of the metal particle.

[0098] When the ink containing the above-mentioned metal particles contains an organic π-conjugated ligand, it is preferable that the organic π-conjugated ligand has at least one substituent selected from the group consisting of a hydroxy group, a carboxy group, an amino group, an alkylamino group, an amide group, an imide group, a phosphonic acid group, a sulfonic acid group, a cyano group, a nitro group, and salts thereof, which is a substituent that makes the metal particles soluble in aqueous solvents and alcoholic solvents. In addition, one or both of the first auxiliary electrode 33 and the second auxiliary electrode 34 preferably contains a binder resin to enhance adhesion to the surface (base) on which they are formed. Examples of such materials include polyester and polyacrylic. The amount of binder resin added is preferably 5% by mass or less of the total amount of the auxiliary electrodes.

[0099] It is preferable that either or both of the first auxiliary electrode 33 and the second auxiliary electrode 34 have voids, and it is more preferable that both the first auxiliary electrode 33 and the second auxiliary electrode 34 have voids. In an auxiliary electrode made of sintered metal particles, voids are generated at the particle contact surfaces. The voids can be confirmed by SEM observation, and an auxiliary electrode in which voids of 5 μm or less can be confirmed by SEM observation is preferable.

[0100] In the electrochromic sheet of this embodiment, the auxiliary electrode has voids, which makes the auxiliary electrode more easily deformable, and therefore peeling and cracking of the sintered body are less likely to occur during heating and bending.

[0101] The average thickness of the first auxiliary electrode 33 and the second auxiliary electrode 34 is preferably 4 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less. More specifically, in a cross section of the first opposing electrode portion 331 and the second opposing electrode portion 341 that is 150 μm wide from the end of the colored region AR in the short direction, the average thickness of the first auxiliary electrode and the second auxiliary electrode is preferably 4 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less. The lower limit is not particularly limited, but examples include 0.01 μm or more, 0.1 μm, and 0.5 μm or more. More specifically, as shown in FIG. 3(b), when the conductive portions 51 and 52 are formed on the lens side surfaces, the average thickness of the first auxiliary electrode 33 and the second auxiliary electrode 34 is preferably 0.5 μm or more. By having an average thickness of 0.5 μm or more, a more stable electrical connection can be achieved, and contact resistance is less likely to increase. The upper and lower limits can be combined in any way.

[0102] By having the average thicknesses of the first auxiliary electrode 33 and the second auxiliary electrode 34 each within the above numerical range, peeling or cracking of the sintered body is less likely to occur during heating and sintering of the auxiliary electrodes or during heating and bending of the EC sheet, and the electrical resistance of the first auxiliary electrode 33 and the second auxiliary electrode 34 is less likely to become high.

[0103] Fig. 4 is a plan view showing an example of the EC sheet 150. As shown in Fig. 4, the first auxiliary electrode 33 and the second auxiliary electrode 34 do not overlap each other in a plan view and are located on opposite sides of the colored region AR in a plan view. Furthermore, the first extraction portion 332 does not overlap with the second transparent electrode 32, and the second extraction portion 342 does not overlap with the first transparent electrode 31.

[0104] The difference between the total length of the first opposing electrode section 331 and the total length of the second opposing electrode section 341 is preferably small, and preferably not more than twice the difference between them. For example, the total length of the first opposing electrode section 331 is preferably more than 50% and less than 200% of the total length of the second opposing electrode section 341, and more preferably 55% to 175%. Furthermore, the total length of the first opposing electrode section 331 is preferably 58% to 165% of the total length of the second opposing electrode section 341, more preferably 61% to 155%, and even more preferably 65% ​​to 145%. The upper and lower limits can be combined in any desired manner.

[0105] The electrochromic sheet of this embodiment may be plastically deformed because peeling or cracking of the sintered body is less likely to occur in the auxiliary electrode. More specifically, the EC sheet may be partially or entirely plastically deformed during heat bending. The shape of the plastically deformed laminate may be a convex shape, a concave shape, or a 3D curved shape.

[0106] (1st electrode protective layer, 2nd electrode protective layer) The electrochromic sheet of this embodiment may further include either or both of a first electrode protective layer 36 and a second electrode protective layer 37. More specifically, the first electrode protective layer 36 is formed in contact with the first auxiliary electrode 33. The first auxiliary electrode 33 is sandwiched between the first transparent electrode 31 and the first electrode protective layer 36. The second electrode protective layer 37 is formed in contact with the second auxiliary electrode 34. The second auxiliary electrode 34 is sandwiched between the second transparent electrode 32 and the second electrode protective layer 37.

[0107] The first electrode protective layer 36, like the first auxiliary electrode 33, is disposed around the colored region AR on the periphery of the first transparent electrode 31 and is in contact with the first auxiliary electrode 33. The second electrode protective layer 37, like the second auxiliary electrode 34, is disposed around the colored region AR on the periphery of the second transparent electrode 32 and is in contact with the second auxiliary electrode 34. When the first electrode protective layer 36 and the second electrode protective layer 37 are conductive and transparent, the first electrode protective layer 36 and the second electrode protective layer 37 can also be formed on the colored region AR.

[0108] The first electrode protection layer 36 may or may not have a protruding portion at a position overlapping the above-described first extraction portion 332, similar to the first extraction portion 332. Similarly, the second electrode protection layer 37 may or may not have a protruding portion at a position overlapping the above-described second extraction portion 342, similar to the second extraction portion 342.

[0109] By forming the first electrode protective layer 36 and the second electrode protective layer 37, the auxiliary electrode can be more easily protected from oxygen, water, and the oxidation-reduction reaction of the EC layer 35. In addition, by forming the first electrode protective layer 36 and the second electrode protective layer 37, the electrical resistance of the auxiliary electrode can be further reduced.

[0110] Materials that are dense, have high barrier properties against oxygen and water, and are resistant to oxidation-reduction reactions can be used for the first electrode protective layer 36 and the second electrode protective layer 37. Specific examples of such materials include inorganic oxides (silicon oxide, zirconia oxide, aluminum oxide, tin oxide, indium oxide, etc.), inorganic nitrides (silicon nitride, aluminum nitride, etc.), inorganic borides (aluminum boride, etc.), metals (Au, Pt, etc.), and carbon. These materials may be used alone or in combination. In particular, when the first electrode protective layer 36 and the second electrode protective layer 37 are conductive and transparent, it is preferable that either or both of the first electrode protective layer 36 and the second electrode protective layer 37 contain indium oxide. As the indium oxide, ITO, IZO, ITO, or In2O3 is more preferable, and ITO is even more preferable.

[0111] The thicknesses of the first electrode protective layer 36 and the second electrode protective layer 37 are adjusted so as to protect the auxiliary electrode and to obtain an electrical resistance value that allows an appropriate voltage to be applied to the EC layer 35. When ITO is used as the material for the first electrode protective layer 36 and the second electrode protective layer 37, the average thicknesses of the first electrode protective layer 36 and the second electrode protective layer 37 are each independently set to, for example, 10 nm or more and 200 nm or less, and preferably 20 nm or more and 100 nm or less.

[0112] (electrochromic layer) As shown in Figures 2 and 3, the EC layer 35 is formed in a three-layer structure having, for example, a first electrochromic layer 351 (first EC layer 351) laminated on the first transparent electrode 31, a second electrochromic layer 352 (second EC layer 352) laminated on the second transparent electrode 32, and an electrolyte layer 353 filled between the first EC layer 351 and the second EC layer 352. Alternatively, the EC layer 35 may be formed as a single layer in which the material of the first EC layer 351, the material of the second EC layer 352, and the material of the electrolyte layer 353 are mixed.

[0113] (First electrochromic layer) The first EC layer 351 is a color-changing layer, and contains as its main material a material that changes color from transparent to color upon oxidation. Examples of materials that change color upon oxidation include known materials that exhibit electrochromism and are used in EC elements, such as polymers of radical polymerizable compounds having a triarylamine structure, bisacridan compounds, triphenylamine, benzidine, Prussian blue complexes, and nickel oxide. The first EC layer 351 may be a polymerized polymer film or a film made of a monomolecular material. The first EC layer 351 may also have a supported particle (so-called Grätzel) structure in which an electrochromic material is adsorbed onto the surface of semiconductor particles or conductive particles such as titanium oxide particles and tin oxide particles.

[0114] Examples of polymers of radically polymerizable compounds having a triarylamine structure include those described in JP-A-2016-45464 and JP-A-2020-138925.

[0115] As the material that is colored by an oxidation reaction, one of these may be used, or two or more of them may be used in combination.

[0116] The average thickness of the first EC layer 351 is preferably 0.1 μm or more and 30 μm or less, and more preferably 0.4 μm or more and 10 μm or less. When the average thickness of the first EC layer 351 is equal to or greater than the lower limit, the color density can be increased. That is, the transmittance change can be increased. Furthermore, when the average thickness is equal to or less than the upper limit, the film quality of the first EC layer 351 can be made more uniform, and the manufacturing cost can be reduced.

[0117] (Second electrochromic layer) The second EC layer 352 is a color-changing layer, and contains as its main material a material that changes color from transparent to color upon reduction. Examples of materials that change color upon reduction include known materials that exhibit electrochromism and are used in EC elements, such as inorganic electrochromic compounds such as tungsten oxide, molybdenum oxide, iridium oxide, and titanium oxide, and organic electrochromic compounds such as viologen-based compounds and dipyridine-based compounds. The second EC layer 352 may be a polymerized polymer film or a monomolecular film. The second EC layer 352 may also have a supported particle (so-called Grätzel) structure in which an electrochromic material is adsorbed onto the surface of semiconductor particles or conductive particles such as titanium oxide particles and tin oxide particles.

[0118] As the material that is colored by a reduction reaction, one of these may be used, or two or more of them may be used in combination.

[0119] The color (color 1) that the first EC layer 351 acquires through an oxidation reaction and the color (color 2) that the second EC layer 352 acquires through a reduction reaction may be the same color tone or different color tones. When color 1 and color 2 have the same color tone, the color density can be increased and the contrast can be further improved. When color 1 and color 2 have different color tones, the color that the EC element 30 acquires is the color obtained by mixing color 1 and color 2.

[0120] By coloring both the first EC layer 351 and the second EC layer 352, the redox dyes of the first EC layer 351 and the second EC layer 352 can simultaneously develop colors, thereby improving the color development speed.

[0121] The average thickness of the second EC layer 352 is preferably 0.2 μm or more and 5.0 μm or less. The average thickness of the second EC layer 352 is more preferably 1.0 μm or more and 4.0 μm or less. When the average thickness of the second EC layer 352 is equal to or more than the above-mentioned lower limit, it is easy to increase the color density. In other words, it is easy to increase the change in transmittance. When the average thickness of the second EC layer 352 is equal to or less than the above-mentioned upper limit, it is possible to further suppress the decrease in visibility due to coloring and further reduce manufacturing costs.

[0122] (electrolyte layer) The electrolyte layer 353 is filled between the first EC layer 351 and the second EC layer 352. The electrolyte layer 353 contains an electrolyte having ion conductivity.

[0123] Examples of electrolytes include inorganic ion salts such as alkali metal salts and alkaline earth metal salts; and supporting salts such as quaternary ammonium salts, acids, and alkalis. Counterions (anions) of the electrolytes include halogens, thiocyanate ions (SCN - ), chlorate ion (ClO3 - ), perchlorate ion (ClO4 - ), tetrafluoroborate ion (BF4 - ), hexafluorophosphate ion (PF6 - ), trifluoromethanesulfonate ion (CF3SO3 - ), trifluoroacetate ion (CF3COO - ), bisfluorosulfonium imide (N(SO2F)2 - ) can be mentioned.

[0124] Specific examples of such electrolytes include LiClO4, LiBF4, LiAsF6, LiPF6, LiCF3SO3, LiCF3COO, KCl, NaClO3, NaCl, NaBF4, NaSCN, KBF4, Mg(ClO4)2, Mg(BF4)2, etc. As the electrolyte, one of these may be used, or two or more of them may be used in combination. When the electrolyte is solid, it is used as an electrolyte solution dissolved in a solvent, or as a solid electrolyte membrane to which a high molecular weight polymer or a gelling agent is further added.

[0125] On the other hand, when the electrolyte is a liquid ionic liquid, it can be used as it is as the electrolyte layer 353. It may also be used as a solid electrolyte membrane. Among ionic liquids, organic ionic liquids have a molecular structure that allows them to remain liquid over a wide temperature range, including room temperature, and are therefore easy to handle.

[0126] The average thickness of the electrolyte layer 353 is preferably 20 μm or more and 100 μm or less, more preferably 30 μm or more and 80 μm or less, and even more preferably 30 μm or more and 70 μm or less.

[0127] [Sealing part] The sealing portion 40 is sandwiched between the first substrate 21 and the second substrate 22 and defines a colored region AR between the first substrate 21 and the second substrate 22. The sealing portion 40 is made of a thermosetting resin or a photocurable resin that adheres to the surfaces of the first substrate 21 and the second substrate 22. Specifically, known materials such as acrylic resin, urethane resin, and epoxy resin can be used. Furthermore, the sealing portion 40 preferably contains an inorganic filler to further reduce linear thermal expansion and oxygen and water permeability. Examples of inorganic fillers include the same inorganic fillers as those used in the first thermal expansion suppression layer 24 and the second thermal expansion suppression layer 25. Furthermore, because high transparency is not required for the sealing portion 40, an opaque filler with a large average particle size, for example, 0.2 μm or greater, can also be used.

[0128] The average thickness of the sealing portion 40 is adjusted according to the average thickness of the EC element 30. The average thickness of the sealing portion 40 is preferably 20 μm or more and 100 μm or less, more preferably 30 μm or more and 80 μm or less, and even more preferably 40 μm or more and 60 μm or less.

[0129] <Laminates, eyeglass lenses> FIG. 5 is an explanatory diagram illustrating a method for manufacturing a lens using the EC sheet 150.

[0130] 5(a), the EC sheet 150 is first bent under heat to curve the EC sheet 150 to match the curvature of the target lens. The bending is performed by, for example, press molding or vacuum forming.

[0131] 5(b), the curved EC sheet 150 is insert-molded as an insert, and a lens material 119 is formed on the concave surface of the EC sheet 150 to obtain a laminate 160. The laminate 160 corresponds to the "laminate" of the present invention. The lens material 119 is processed as described below to become the lens body 115.

[0132] The lens material 119 has a visible light transmittance and may be made of a thermoplastic resin known as a material for optical members.

[0133] It is preferable that the material of the lens material 119 is the same as or the same as the main material of the substrate (first substrate 21 or second substrate 22) that contacts the lens material 119 in the EC sheet 150, as this facilitates close contact between the EC sheet 150 and the lens material 119. Furthermore, if the materials of the substrate and the lens material 119 are the same as or the same, the difference in refractive index between the substrate and the lens material 119 can be reduced, and light scattering and reflection at the interface between the EC sheet 150 and the lens material 119 can be suppressed. The difference in refractive index between the substrate and the lens material 119 is preferably 0.2 or less, and more preferably 0.1 or less.

[0134] The thickness of the lens material 119 is preferably, for example, 1.5 mm or more and 20 mm or less. By setting the thickness of the lens material 119 within this range, it is possible to achieve both high strength and light weight for the obtained lens.

[0135] Next, the surface of the lens material 119 is polished, and the surfaces of the EC sheet 150 and the lens material 119 are hard-coated and anti-reflection treated. After that, a through hole exposing the first extraction portion 332 and a through hole exposing the second extraction portion 342 are formed in the sealing portion 40 at positions overlapping with the first extraction portion 332 and the second extraction portion 342. A conductive portion 51 electrically connected to the first extraction portion 331 and a conductive portion 52 electrically connected to the second extraction portion 341 are formed in the through holes.

[0136] 3(a) can be formed by a conductive paste filled in the through-holes or a conductive cylindrical member inserted in the through-holes. Alternatively, any known material can be used as long as it is formed in the through-holes and can be electrically connected to the first auxiliary electrode 33 (first extraction portion 332) and the second auxiliary electrode 34 (second extraction portion 342). The conductive portions 51 and 52 in the form of FIG. 3(b) can be easily formed by applying a conductive paste to the side surface of the trimmed lens 110 (FIG. 5(c)).

[0137] 5(c), the laminate 160 is trimmed to a shape corresponding to the rim portion 121 of the above-described sunglasses 100. At this time, trimming of the periphery of the first extraction portion 332 and the second extraction portion 342 is performed using, for example, a rotating cylindrical grindstone or milling.

[0138] By such processing, a lens 110 is obtained, which includes an EC portion 111 obtained by cutting the EC sheet 150 and a lens body 115 in which the EC portion 111 is laminated (see FIG. 1). In FIG. 5, when cutting the laminate 160, the lens 110 is obtained by cutting along the outer peripheries of the first auxiliary electrode 33 and the second auxiliary electrode 34 of the EC sheet 150. The obtained lens 110 corresponds to the "eyeglass lens" of the present invention.

[0139] The lens material 119 of the laminate 160 is processed into the lens body 115 by trimming along the outer peripheries of the first auxiliary electrode 33 and the second auxiliary electrode 34. The lens body 115 has a protrusion 115a having the same shape as the first extraction portion 332 and the second extraction portion 342 in a plan view.

[0140] If the first and second extraction portions 332 and 342 of the EC sheet 150 are configured not to protrude from the auxiliary electrodes to the outer periphery, the lens body 115 may not have the protrusion 115a.

[0141] The obtained lens 110 is combined with the frame 120 shown in Fig. 1. At this time, the first extraction portion 332 and the second extraction portion 342 of the EC portion 111 are electrically connected to the frame 120 via the conductive portions provided thereon. In this embodiment, the first extraction portion 332 and the second extraction portion 342 are electrically connected to external terminals (not shown) provided on the temple portion 123 or the bridge portion 122 of the frame 120, and are connected to the battery 126. This results in the sunglasses 100.

[0142] Since it is easier to hide the first auxiliary electrode 33, the second auxiliary electrode 34, and the sealing portion 40 of the EC sheet 150, the eyeglasses (sunglasses 100) to which the lenses 110 are applied are preferably designed with a frame rather than a frameless design that does not have a frame surrounding the periphery of the lens. For the same reason, eyeglasses to which the lenses 110 are applied are preferably designed with a frame that surrounds the entire periphery of the lens rather than a half-rim type design.

[0143] The shape of the lens 110 is not particularly limited and can be appropriately adopted depending on the design. For example, the lens shape can be a shape that matches known frame shapes such as Wellington, Thermont (brow), Boston, teardrop, Lexington, square, round, oval, and Fox.

[0144] The laminate, eyeglass lens, and eyeglasses having the above-described configurations have high quality and can develop and fade colors without delay due to the inclusion of the electrochromic sheet.

[0145] In this embodiment, sunglasses 100 are shown as an example of eyeglasses, but the present invention is not limited to this. Lenses 110 may be applied to, for example, goggles that protect the eyes from wind, rain, dust, chemicals, etc. Alternatively, lenses 110 may be applied to a wearable device, such as smart glasses, that is worn on the user's head with lenses 110 positioned in front of the user's eyes.

[0146] In addition, in the present embodiment, the EC layer 35 includes the first EC layer 351 and the second EC layer 352, but this is not limitative. Even if the EC layer 35 includes only one of the first EC layer 351 and the second EC layer 352, the effects of the present invention can be achieved.

[0147] While the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to these examples. The shapes and combinations of the components shown in the above examples are merely examples, and various modifications can be made based on the design, specifications, etc., without departing from the spirit of the present invention. [Example]

[0148] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. [Example 1] The EC sheet 150 of Example 1 was produced by the method described below.

[0149] 1. Preparation of the first substrate 21 First, a polycarbonate sheet (product name: PC2151, manufactured by Teijin Limited) having a thickness of 0.3 mm, a square shape with one side measuring 100 mm, and a glass transition temperature of 146° C. was prepared as the first resin substrate 23.

[0150] An acid-modified epoxy urethane acrylate oligomer resin (product name: ZCR6001H, manufactured by Nippon Kayaku Co., Ltd., softening temperature after curing: 198°C), which is a curable resin material, was prepared as the main material for the first thermal expansion suppression layer 24. In addition, an inorganic particle propylene glycol monomethyl ether dispersion (product name: PGM-AC2140Y, manufactured by Nissan Chemical Co., Ltd., methacrylic surface treatment, average particle size: 10 nm to 15 nm, SiO2) was prepared as the inorganic filler to be contained in the curable resin.

[0151] The inorganic filler was added to the curable resin so that the content of the inorganic particles was 150% by mass relative to the total amount of the curable resin, and then a photoinitiator (product name: Omnirad TPO H, manufactured by IGM Resins BV) was added in an amount of 4% by mass relative to the total amount of the curable resin to prepare a coating solution.

[0152] The resulting coating solution was diluted with 2-ethoxyethanol and then coated onto the surface of a polycarbonate sheet using a bar coater. The coating solution was then dried at 80°C for 5 minutes and cured by UV irradiation to form a first thermal expansion suppressing layer 24 with an average thickness of 2 µm.

[0153] Next, the first substrate 21 having the first thermal expansion suppressing layer 24 formed on the first resin substrate 23 was cut into a sheet shape (minor axis 55 mm, major axis 75 mm) shown in FIG.

[0154] 2. Fabrication of Electrolyte Layer 353 First, binder resin 1, binder resin 2, and ionic liquid 1 described below were prepared. Binder resin 1: urethane acrylate (product name: UXF4002, manufactured by Nippon Kayaku Co., Ltd.) Binder resin 2: Crosslinked polymer having polymethyl methacrylate (PMMA) chains (product name: AA-6, manufactured by Toagosei Co., Ltd.) Ionic liquid 1: 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIMFS) (Kanto Chemical Co., Ltd.)

[0155] Next, binder resin 1, binder resin 2, and ionic liquid 1 were mixed in a mass ratio of binder resin 1:binder resin 2:ionic liquid 1=18:7:75.

[0156] Furthermore, a photopolymerization initiator (product name: IRGACURE 184, manufactured by BASF Ltd.) was mixed in such that the amount was 0.5% by mass relative to the total amount of binder resin 1 and binder resin 2 to prepare an electrolyte solution.

[0157] The obtained electrolyte solution was applied to the surface of a release-treated PET film (product name: NP75C, manufactured by PANAC Corporation). Furthermore, a release-treated PET film (NP75A, manufactured by PANAC Corporation) was placed on top of the PET film to which the electrolyte solution had been applied. The two obtained PET films were cured by UV irradiation to produce an electrolyte sheet laminated with two PET films.

[0158] Next, the obtained electrolyte sheet was cut with a Pinnacle (registered trademark) blade into an electrolyte layer shape corresponding to FIG. 2 to obtain an electrolyte layer 353. The area of ​​the electrolyte layer 353 corresponding to the colored region AR was 1250 mm 2 It was.

[0159] 3. Fabrication of the first transparent electrode 31 On the obtained first substrate 21, a first transparent electrode 31 made of ITO with a thickness of 130 nm was obtained using a sputtering device (manufactured by Solaris Evatec Co., Ltd.).

[0160] 4. Preparation of the first auxiliary electrode 33 Next, a water-based Ag nanoparticle ink containing an organic π-conjugated ligand (product name: Dry Cure Ag-JB 0420B, manufactured by C-INK) was prepared. The water-based Ag nanoparticle ink was inkjet coated (precision core i1600, a machine equipped with an Epson head) to an average thickness of 2 μm, and then heated and baked in an oven at 120° C. for 30 minutes to form a first auxiliary electrode 33.

[0161] 5. Fabrication of the first EC layer 351 Polyethylene glycol diacrylate (trade name: PEG400DA, manufactured by Nippon Kayaku Co., Ltd.), a photoinitiator (trade name: IRGACURE 184, manufactured by BASF Ltd.), a compound represented by the following formula (I) (Compound I), and cyclohexanone were mixed in a mass ratio of polyethylene glycol diacrylate:photoinitiator:compound I:cyclohexanone = 76:3:170:860.

[0162] [ka] (wherein Me represents a methyl group)

[0163] The resulting mixed solution was inkjet coated on the first transparent electrode 31 to form a coating film in the region corresponding to the first EC layer 351 shown in FIG. 3(b). The coating film was then exposed to UV light in a nitrogen atmosphere to obtain the first EC layer 351 containing compound I. The average thickness of the first EC layer 351 was 1 μm.

[0164] 6. Fabrication of the second substrate 22 The second substrate 22 was obtained in the same manner as in the first substrate 21.

[0165] 7. Fabrication of second transparent electrode 32 The second transparent electrode 32 was obtained in the same manner as in the first transparent electrode 31 .

[0166] 8. Preparation of the second auxiliary electrode 34 The second auxiliary electrode 34 was obtained in the same manner as in the first auxiliary electrode 33.

[0167] 9. Fabrication of second EC layer 352 5.50 g of tin oxide sol solution (trade name: Celnax CX-S510M, manufactured by Nissan Chemical Industries, Ltd.) was mixed with 1.00 g of an ethanol solution containing 10% by mass of ethyl cellulose (viscosity: 10 mPa s), 0.50 g of tin(IV) tetra(t-butoxide), and 9.05 g of terpineol. The mixture was then subjected to ultrasonic treatment for 2 minutes using an ultrasonic homogenizer, and the volatile components were removed using an evaporator to obtain a paste.

[0168] The obtained paste was screen-printed to an average thickness of 2 μm on the second transparent electrode 32 in the area corresponding to the second EC layer 352 in FIG. 3(b). The screen-printed paste was then dried at 80°C and subjected to UV ozone treatment at 90°C for 20 minutes to obtain a porous tin oxide particle film.

[0169] Next, a 2,2,3,3-tetrafluoropropanol solution containing 1.5 mass % of a compound represented by the following formula (II) (compound II) was prepared.

[0170] [ka]

[0171] The 2,2,3,3-tetrafluoropropanol solution was spin-coated onto the tin oxide particle film, and annealed at 80° C. for 10 minutes to obtain a second EC layer 352 in which the compound II was supported on the tin oxide particle film.

[0172] 10. Preparation of EC sheet 150 An electrolyte layer 353 was attached to the surface of the second EC layer 352. Next, a sealing material made of epoxy acrylate resin (product name: Photolec S-WF17, manufactured by Sekisui Material Solutions Co., Ltd.) was applied using a dispenser to a position surrounding the periphery of the side surface of the second EC layer 352. Next, the electrolyte layer 353 attached to the second EC layer was attached to the surface of the first EC layer 351.

[0173] The obtained laminate was pressed for 60 seconds to spread the sealing material, thereby covering the side surfaces of the first EC layer 351 and the second EC layer 352 with the sealing material. Next, for temporary curing, the obtained laminate was irradiated with ultraviolet light (3 J / cm 2 ) was irradiated. Next, as the main curing, the temporarily cured laminate was subjected to a heat curing treatment at 100° C. for 1 hour, thereby forming the sealing portion 40. By the above operations, an EC sheet of Example 1 having the arrangement shown in FIG. 4 was obtained.

[0174] (EC sheet evaluation) 1. Evaluation of the appearance of the auxiliary electrode When the first auxiliary electrode 33 and the second auxiliary electrode 34 of the EC sheet of Example 1 were observed under a microscope, no peeling or cracks were found.

[0175] Next, the EC sheet of Example 1 was molded into a spherical shape as shown in Fig. 5(a) under conditions of a mold curvature radius of 130 mm and a mold temperature of 146°C. Microscopic observation of the first auxiliary electrode 33 and the second auxiliary electrode 34 of the EC sheet of Example 1 molded into a spherical shape revealed no peeling or cracks.

[0176] 2. Evaluation of electrode resistance An EC lens sheet was fabricated to evaluate the electrical resistance. First, the EC sheet of Example 1 was cut into a lens shape as shown in Fig. 5(c). Silver paste (product name: CN7120, manufactured by Kaken Tech Co., Ltd.) was applied to the side surfaces of the obtained EC lens sheet, and then cured and dried. That is, conductive portions 51 and 52 as shown in Fig. 3(b) were formed on the first auxiliary electrode 33 and the second auxiliary electrode 34, respectively, to obtain the EC lens sheet of Example 1.

[0177] The contact resistance of the EC lens sheet of Example 1 was measured by the following AC impedance method, and the contact resistance was calculated from the point where Z'' on the Nyquist diagram was 0. As a result, as shown in Figures 6(a) and 6(b), the contact resistance was 30Ω.

[0178] The measurement conditions for the AC impedance method are as follows: Measurement device: Modulab XM (Solartron Analytical) Applied voltage: 0V Amplitude: 10mV Frequency response: 0.1Hz to 1MHz Measurement temperature: 25℃

[0179] 3. Evaluation of dimming operation A power source was connected to the conductive portions 51 and 52 of the EC lens sheet of Example 1, and a positive voltage of 2 V was applied to the conductive portion 51. As a result, the colored area AR changed from transparent to blue. Next, the conductive portions 51 and 52 were short-circuited, and the blue color of the colored area AR disappeared. These results confirmed that the EC sheet of Example 1 has a light-adjusting function.

[0180] [Example 2] (EC sheet production) An EC sheet of Example 2 was obtained in the same manner as in the EC sheet of Example 1, except that the inkjet-coated auxiliary electrode was dried at 95°C for 30 minutes and then photo-baked with an infrared laser. The laser light source was CW, wavelength 940 nm, 360 W, irradiation spot size: 80 mm × 2 mm (laser light source L13920-711 manufactured by Hamamatsu Photonics K.K.). An irradiation unit A133933-13W (manufactured by Hamamatsu Photonics K.K.) was used, and the scanning speed was set to 150 mm / sec.

[0181] (EC sheet evaluation) 1. Evaluation of the appearance of the auxiliary electrode When the first auxiliary electrode 33 and the second auxiliary electrode 34 of the EC sheet of Example 2 were observed under a microscope, no peeling or cracks were found.

[0182] Next, the EC sheet of Example 2 was molded into a spherical shape in the same manner as the EC sheet of Example 1. As a result of observing the first auxiliary electrode 33 and the second auxiliary electrode 34 of the EC sheet of Example 1 molded into a spherical shape under a microscope, no peeling or cracks were confirmed.

[0183] 2. Evaluation of electrode resistance Using the EC sheet of Example 1, an EC lens sheet of Example 2 was produced in the same manner as in Example 1. Using the obtained EC lens sheet of Example 2, the contact resistance was determined in the same manner as in Example 1. As a result, the contact resistance was 30Ω.

[0184] 3. Evaluation of dimming operation The EC lens sheet of Example 2 was used to evaluate the light control function in the same manner as in Example 1. As a result, it was confirmed that the EC sheet of Example 2 had a light control function. [Comparative Example 1] (EC sheet production) The EC sheet of Comparative Example 1 was produced in the same manner as the EC sheet of Example 1, except that the first thermal expansion suppression layer 24 and the second thermal expansion layer 25 were not formed, and the first auxiliary electrode 33 and the second auxiliary electrode 34 were formed by sputtering using a silver alloy (APC, manufactured by Furuya Metal Co., Ltd.). The silver alloy film had a thickness of 200 nm and was patterned using mask sputtering (manufactured by Solaris Evatec Co., Ltd.).

[0185] (EC sheet evaluation) 1. Evaluation of the appearance of the auxiliary electrode When the first auxiliary electrode 33 and the second auxiliary electrode 34 of the EC sheet of Comparative Example 1 were observed under a microscope, no peeling or cracks were found.

[0186] Next, the EC sheet of Comparative Example 1 was molded into a spherical shape in the same manner as the EC sheet of Example 1. As a result of observing the first auxiliary electrode 33 and the second auxiliary electrode 34 of the EC sheet of Comparative Example 1 molded into a spherical shape with a microscope, cracks were confirmed.

[0187] 2. Evaluation of electrode resistance Using the EC sheet of Comparative Example 1, an EC lens sheet of Comparative Example 1 was produced in the same manner as in Example 1. The contact resistance was measured using the obtained EC lens sheet of Comparative Example 1 in the same manner as in Example 1, but the contact resistance was so large that normal measurement results could not be obtained.

[0188] 3. Evaluation of dimming operation Using the EC lens sheet of Comparative Example 1, the light control operation was evaluated in the same manner as in Example 1. As a result, it was confirmed that the electrochromic layer did not react and had no light control function. [Explanation of symbols]

[0189] 21...first substrate, 22...second substrate, 23...first resin substrate, 24...first thermal expansion suppressing layer, 25...second thermal expansion suppressing layer, 26...second resin substrate, 30...electrochromic element (EC element), 31...first transparent electrode, 32...second transparent electrode, 33...first auxiliary electrode, 34...second auxiliary electrode, 35...electrochromic layer (EC layer), 36...first electrode protection layer, 37...second electrode protection layer, 40...sealing portion, 40a, 40b...through hole, 51, 52...conductive portion, 100...sunglasses, 110...lens, 111...electrochromic portion (EC portion), 11 5...lens body, 115a...protrusion, 119...lens material, 120...frame, 121...rim portion, 122...bridge portion, 123...temple portion, 124...nose pad portion, 125...switch, 126...battery, 150...electrochromic sheet (EC sheet), 160...laminated body, 331...first opposing electrode portion, 332...first extraction portion, 341...second opposing electrode portion, 342...second extraction portion, 351...first electrochromic layer (first EC layer), 352...second electrochromic layer (second EC layer), 353...electrolyte layer, AR...colored region

Claims

1. a first substrate; a second substrate; an electrochromic element sandwiched between the first substrate and the second substrate; a sealing portion sandwiched between the first substrate and the second substrate and defining a colored region set between the first substrate and the second substrate, the first substrate includes a first resin substrate and a first thermal expansion suppression layer provided on the first resin substrate; The electrochromic element includes a first transparent electrode provided on the first thermal expansion suppressing layer side of the first substrate; a first auxiliary electrode disposed around the colored region, electrically connected to the first transparent electrode, and including a sintered body of metal particles; a second transparent electrode provided on the second substrate; an electrochromic layer that is sandwiched between the first transparent electrode and the second transparent electrode, that is disposed in the coloring region, and that changes color upon application of a voltage; Electrochromic sheet.

2. the second substrate further includes a second resin substrate and a second thermal expansion suppression layer provided on the second resin substrate, The electrochromic element further includes a second auxiliary electrode disposed around the colored region, electrically connected to the second transparent electrode, and including the sintered body. The electrochromic sheet according to claim 1 .

3. Further, the semiconductor device has either one or both of a first electrode protection layer and a second electrode protection layer, the first electrode protection layer is in contact with the first auxiliary electrode, the first auxiliary electrode is sandwiched between the first transparent electrode and the first electrode protection layer, the second electrode protection layer is in contact with the second auxiliary electrode, The electrochromic sheet according to claim 2 , wherein the second auxiliary electrode is sandwiched between the second transparent electrode and the second electrode protection layer.

4. the first auxiliary electrode has a first opposing electrode portion extending along a part of the outer periphery of the colored region, the second auxiliary electrode has a second opposing electrode portion extending along another part of the outer periphery of the colored region, the second opposing electrode portion is on the opposite side of the colored region from the first opposing electrode portion and faces the first opposing electrode portion; 3. The electrochromic sheet according to claim 2, wherein a width of a portion including at least one end of the first opposing electrode portion and the second opposing electrode portion is 0.1 mm or more and 2.0 mm or less.

5. 5. The electrochromic sheet according to claim 4, wherein the first auxiliary electrode and the second auxiliary electrode have an average thickness of 4 μm or less in a cross section of the first opposing electrode portion and the second opposing electrode portion that is 150 μm wide from the end of the colored region in the short direction.

6. 3. The electrochromic sheet according to claim 2, wherein one or both of the first thermal expansion suppressing layer and the second thermal expansion suppressing layer is made of a curable resin containing a filler.

7. 3. The electrochromic sheet according to claim 2, wherein either or both of the first auxiliary electrode and the second auxiliary electrode further contain an organic π-conjugated ligand.

8. The electrochromic sheet according to claim 2 , wherein one or both of the first auxiliary electrode and the second auxiliary electrode has a gap.

9. one or both of the first resin substrate and the second resin substrate contains a thermoplastic resin; 3. The electrochromic sheet according to claim 2, wherein the glass transition temperature of the thermoplastic resin is 200° C. or lower.

10. 3. The electrochromic sheet according to claim 2, wherein the first auxiliary electrode and the second auxiliary electrode are electrically connected to terminals for applying voltages independently in cross sections of the first auxiliary electrode and the second auxiliary electrode in the thickness direction.

11. 3. The electrochromic sheet according to claim 1, wherein either or both of the first transparent electrode and the second transparent electrode contain indium oxide.

12. 3. The electrochromic sheet according to claim 1 or 2, which has been plastically deformed.

13. The electrochromic sheet according to claim 1 or 2; and a lens material on which the electrochromic sheet is laminated.

14. an electrochromic section obtained by cutting the electrochromic sheet according to claim 2 along the outer peripheries of the first auxiliary electrode and the second auxiliary electrode; and a lens body on which the electrochromic portion is laminated.

15. The eyeglass lens according to claim 14; a frame for holding the eyeglass lenses; The lens body is electrically connected to the frame of the eyeglasses.

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