Electrochromic lenses and electrochromic devices
Patent Information
- Application Number
- JP2023096391
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2023-06-12
- Publication Date
- 2025-03-05
- Estimated Expiration
- 2043-06-12
AI Technical Summary
【0011】 本発明は、エレクトロクロミックレンズとしての性能を保持しつつ良好な外観が得られるエレクトロクロミックレンズを提供する。
Smart Images

Figure 0007639850000002 
Figure 0007639850000003 
Figure 0007639850000004
Abstract
Description
[Technical field]
[0001] The present invention relates to electrochromic lenses and electrochromic devices, and more particularly to methods of using electrochromic lenses, electrochromic devices and electrochromic sheeting. [Background technology]
[0002] In recent years, lenses having optical sheets on their surfaces, such as polarizing films with polarizing properties or half-mirror layers that can impart design features by selectively reflecting light in a specific wavelength range, have been proposed as lenses for use in eyewear such as spectacles and sunglasses.
[0003] On the other hand, electrochromic elements are known as elements that utilize electrochromism, a phenomenon in which a reversible redox reaction occurs when a voltage is applied, causing a reversible change in transmittance. For example, an electrochromic element can be colored by applying a positive voltage to it, and can be decolored and made transparent by applying a negative voltage, so that by providing a switch that can switch between applying a positive voltage and a negative voltage, it becomes possible to color and decolor the electrochromic element at any time.
[0004] 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 by the flip of a switch.
[0005] For example, Patent Document 1 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. [Prior art documents] [Patent documents]
[0006] [Patent Document 1] International Publication No. 2017 / 009563 Summary of the Invention [Problem to be solved by the invention]
[0007] The inventors have studied the technology disclosed in Patent Document 1 and found that the technology focuses on limiting the width of the seal (sealing material) surrounding the cavity to less than 1000 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 moisture barrier property and oxygen gas barrier property of the seal. As a result, it has been found that the color development and decolorization performance of the electrochromic sheet, such as color tone, speed, and color development stability, may be reduced. [Means for solving the problem]
[0008] The present inventors have embodied new requirements for electrochromic lenses that provide good appearance while maintaining the performance required for electrochromic lenses, and have completed the present invention.
[0009] According to the present invention, the following electrochromic lens and related techniques are provided.
[0010] [1] An electrochromic element; a sealing material that covers a side surface of the electrochromic element; a pair of transparent substrate layers sandwiching the electrochromic element and the sealing material; An electrochromic lens comprising: Electrochromic lenses that meet the following requirement a. (Requirement a) 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, 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, and S2 / S (percentage) is 1 to 40%, The second region is defined as a length of 4 mm at any position on the inner circumferential edge of the sealing material, La, and the area of the region occupied by the sealing material including La is defined as Sa (mm 2 ) and Sa / La is Wa (mm), this includes the area where Wa (mm) is 1.5 mm or more. [2] The electrochromic lens according to [1], The electrochromic lens has a through electrode that penetrates the sealing material in the second region. [3] An electrochromic lens according to [1] or [2], The electrochromic lens has a gripping portion at the second region. [4] An electrochromic lens according to any one of [1] to [3], The electrochromic lens, wherein the sealing material is formed from a resin composition including a curable resin. [5] An electrochromic lens according to any one of [1] to [4], 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 [5], The electrochromic lens, wherein the electrolyte layer is a solid or a gel. [7] An electrochromic lens according to any one of [1] to [6], The electrochromic lens further comprises an electrode layer between the transparent substrate layer and the electrochromic element. [8] An electrochromic lens according to any one of [1] to [7], The electrochromic lens, 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 an electrochromic lens described in any one of [1] to [8].
[10] An electrochromic element; a sealing material that covers a side surface of the electrochromic element; a pair of transparent substrate layers sandwiching the electrochromic element and the sealing material; A method for using an electrochromic sheet, comprising: A method for using an electrochromic sheet, comprising the step of processing the electrochromic sheet into an electrochromic lens that satisfies the following requirement b. (Requirement b) The length of the inner 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 layer 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, 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, and S2 / S (percentage) is 1 to 40%, The second region is defined as a length of 4 mm at any position on the inner circumferential edge of the sealing material, La, and the area of the region occupied by the sealing material including La is defined as Sa (mm 2 ) and Sa / La is Wa (mm), this includes the area where Wa (mm) is 1.5 mm or more. Effect of the Invention
[0011] The present invention provides an electrochromic lens that can provide a good appearance while maintaining the performance required for an electrochromic lens. [Brief description of the drawings]
[0012] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an electrochromic sheet according to an embodiment of the present invention. [Diagram 2] 1A to 1C are schematic diagrams showing a method for manufacturing a lens using the electrochromic sheet of the present embodiment. [Diagram 3] 1 is a schematic cross-sectional view of an electrochromic lens according to an embodiment of the present invention as viewed from the side. [Figure 4] FIG. 2 is a schematic plan view showing an example of a lens using the electrochromic sheet of the present embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. In order to avoid complexity, when there are multiple identical components in the same drawing, only one of them may be marked with a symbol, and not all of them may be marked with a symbol. All drawings are for illustrative purposes only. The shape and dimensional ratio of each component in the drawings do not necessarily correspond to the actual product.
[0014] In this specification, the expression "a to b" in the description of a numerical range means a or more and b or less, unless otherwise specified. For example, "1 to 5 mass%" means "1 mass% or more and 5 mass% or less." In addition, the lower limit and upper limit of a numerical range can be arbitrarily combined with the lower limit and upper limit of another numerical range.
[0015] Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more kinds.
[0016] In this embodiment, "covering" is not limited to being continuous, but may include some discontinuous portions.
[0017] The electrochromic lens of this embodiment is manufactured to correspond to a desired lens by using an electrochromic sheet. First, the electrochromic sheet 100 of the present embodiment will be described.
[0018] <Electrochromic sheet> FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of an electrochromic sheet 100. As shown in FIG. As shown in FIG. 1, the electrochromic sheet 100 comprises a laminate (hereinafter also referred to as "electrochromic element 10") in which an electrolyte layer 4, a first electrochromic layer 3, and a second electrochromic layer 5 are laminated in that order, a sealing material 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 top and bottom surfaces of the electrochromic element 10 and the sealing material 8 therebetween. In other words, the electrochromic sheet 100 comprises a first electrochromic layer 3, an electrolyte layer 4, a second electrochromic layer 5, and a second transparent substrate layer 7, which are sequentially stacked on a first transparent substrate layer 1, and the sides of the first electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 are each covered with a sealing material 8.
[0019] In this embodiment, the electrochromic sheet 100 further has a first electrode 2 between the first transparent substrate layer 1 and the first electrochromic layer 3, and a second electrode 6 between the second transparent substrate layer 7 and the second electrochromic layer 5.
[0020] Furthermore, 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, and reaches from the first auxiliary electrode layer 21 provided on the first electrode 2 to the second transparent substrate layer 7. Similarly, the second columnar conductive portion 62 penetrates the sealing material 8, and reaches from the second auxiliary electrode layer 61 provided on the second electrode 6 to the first transparent substrate layer 1.
[0021] In this embodiment, the electrochromic sheet 100 will be described taking as an example a case 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 provided. Details of each component will be described later.
[0022] Furthermore, while FIG. 1 shows a portion of an electrochromic sheet 100 that focuses on a single electrochromic element 10 and the sealing material 9 that surrounds it, the electrochromic sheet 100 may also be one in which multiple electrochromic elements 10 are partitioned by sealing material 8 that covers the sides of each electrochromic element 10.
[0023] Next, a method for manufacturing the electrochromic lens 300 of this embodiment using an electrochromic sheet will be described.
[0024] <Manufacturing method of electrochromic lenses> Hereinafter, each step of the method for producing the lens 30 including the curved sheet 120 obtained by curvedly forming the electrochromic sheet 100 of the present invention will be described in detail. Fig. 2 is a schematic diagram showing a method for manufacturing a lens using the electrochromic sheet of this embodiment. The upper side of Fig. 2 is referred to as "top" and the lower side of Fig. 2 is referred to as "bottom" in the following description. As shown in Fig. 2, the electrochromic sheet 110 has a plurality of electrochromic elements 10 and a sealant 8 surrounding the electrochromic elements 10, in other words, the electrochromic sheet 110 has a plurality of electrochromic elements 10 partitioned by the sealant 8.
[0025] (Process 1) First, protective films 50 (masking tape) are attached to both sides of the electrochromic sheet 110 to obtain a connecting sheet laminate 210 in which the protective films 50 are attached to both sides of the electrochromic sheet 110 (see FIG. 2(a)).
[0026] (Process 2) 2(b), the connecting sheet laminate 210 is punched in its thickness direction so as to correspond to each electrochromic element 10, thereby obtaining an element laminate 250 in which the connecting sheet laminate 210 is singulated into pieces each having a substantially rectangular shape in a plan view. That is, the electrochromic sheet 100 is obtained, singulated into a substantially rectangular shape corresponding to each electrochromic element 10 and the sealing material 9 covering the outer edge thereof with the protective film 50 attached to both sides (see FIG. 1).
[0027] 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.
[0028] (Step 3) 2(c), the separated element stack 250 is subjected to a thermal bending process under heating to form the element stack 250 into a curved element stack 220 having a curved shape with one surface side being a curved concave surface and the other surface side being a curved convex surface. This allows the flat electrochromic sheet 100 to be formed into a curved sheet 120 having a curved shape with the protective films 50 attached to both surfaces.
[0029] This heat bending is usually carried out by press forming or vacuum forming. At this time, the heating temperature (molding temperature) of the element stack 250 (electrochromic sheet 100) is preferably set to about 110° C. or higher and 170° C. or lower, and more preferably about 130° C. or higher and 160° C. or lower. By setting the heating temperature within this range, it is possible to prevent alteration or deterioration of the electrochromic sheet 100, while softening or melting the electrochromic sheet 100, and reliably thermally bending the electrochromic sheet 100 into the curved sheet 120 having a curved shape.
[0030] (Step 4) Next, the protective film 50 is peeled off from the curved sheet 120 that has been thermally bent. Thereafter, as shown in FIG. 2(d), the curved concave surface of the mold 40 having a curved concave surface formed in a curved shape is brought into contact with the curved convex surface of the curved sheet 120, and in a state where the curved sheet 120 is adsorbed, a resin layer 35 (molding layer) mainly made of a resin material is injection molded on the curved concave surface of the curved sheet 120 by, for example, insert injection molding. More specifically, in a state where the curved sheet 120 is adsorbed on the lower mold 42, an upper mold 41 is attached, and in a cavity 43 that is a space formed by the lower mold 42 and the upper mold 41, a resin layer 35 mainly made of a resin material is molded by, for example, insert injection molding. That is, the constituent material of the resin layer 35 in a molten state is cooled and solidified while in contact with the curved concave surface of the curved sheet 120, and the resin layer 35 is molded in a state of direct contact with the curved concave surface of the curved sheet 120 without an adhesive layer or the like being interposed therebetween. In this way, the base lens 30 including the thermally bent curved sheet 120 and the resin layer 35 is manufactured.
[0031] When the resin layer 35 is injection molded, the heating temperature (molding temperature) of the constituent material of the resin layer 35 to make it in a molten state is appropriately set according to the type of the constituent material of the resin layer 35, but when the constituent material of the resin layer 35 is the same or identical to the constituent material of the transparent base material layers (first transparent base material layer 1 and second transparent base material layer 7) of 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.
[0032] Among the insert injection molding methods, the injection compression molding method is preferably used. The injection compression molding method involves injecting a resin material for forming the resin layer 35 into the mold 40 at low pressure, and then closing the mold 40 at high pressure to apply a compressive force to the resin material, so that the resin layer 35 as the molded body, and in turn the base lens 30, are less likely to suffer from molding distortion or optical anisotropy due to the local orientation of the resin molecules during molding, and is therefore preferably used. Furthermore, by controlling the mold compression force that is uniformly applied to the resin material, the resin material can be cooled at a constant specific volume, so that the resin layer 35 can be obtained with high dimensional accuracy.
[0033] Then, a trimming process is performed to cut the edge of the manufactured base lens 30. In this way, an electrochromic lens 300 of a desired shape can be obtained, with the sealing material 8 as the outer edge and the electrochromic element 10 inside (FIG. 3).
[0034] <Electrochromic lenses> The electrochromic lens 300 of the present embodiment comprises an electrochromic element 10, a sealing material 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 sealing material 8, and satisfies the following requirement a.
[0035] (Requirement a) The length of the inner edge of the sealant 8 is L (mm), and the area of the region occupied by the sealant 8 is S (mm), measured in orthogonal projection when the sealant 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. 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, 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, and S2 / S (percentage) is 1 to 40%, The second region is defined as a length of 4 mm at any position on the inner circumferential edge of the sealing material 8, 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), this includes the area where Wa (mm) is 1.5 mm or more.
[0036] That is, the electrochromic lens 300 has a predetermined ratio of an area where the width of the sealant 8 located at the outer edge in orthogonal projection is 1 mm or less and an area where the width is 1.5 mm or more. This allows the sealant 8 to maintain moisture and oxygen barrier properties while reducing the deterioration 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. That is, by having an area where the sealant 8 is narrow and an area where the sealant 8 is wide, the sealant 8 is less visible in the narrow area, improving the design of the appearance, while the sealant 8 can exert a better barrier function in the wide area, so that the electrochromic lens 300 as a whole can easily maintain its performance while obtaining a good appearance.
[0037] 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.
[0038] 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%.
[0039] 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.
[0040] The second region is a region in which W is 1.5 mm or more, but W may be 2.0 mm or more, or may be 3.0 mm or more.
[0041] For example, in the second region, when W is 3.0 mm or more, it is preferable that S2 / S (percentage) is 1 to 10%.
[0042] Moreover, the electrochromic lens 300 preferably has a through electrode (the first columnar conductive portion 22 or the 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 fading performance while suppressing deterioration of the appearance of the electrochromic lens 300. The details of the first columnar conductive portion 22 or the second columnar conductive portion 62 will be described later, but when processed into a spectacle lens shape, they are positioned so as to be exposed at the end of the spectacle lens. Specifically, the bridge side of the spectacle lens or the temple side of the spectacle lens (the side opposite to the bridge side) can be mentioned. In other words, the second region is preferably located near the connection part with the spectacle lens bridge or near the connection part with the spectacle lens temple.
[0043] Moreover, the electrochromic lens 300 preferably has a gripping portion in the second region. The gripping portion refers to a groove or a convex portion for fitting the electrochromic lens 300 into an eyewear frame, or a groove or a convex portion 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 upper part of the frame and fitting a convex gripping portion therein, or may be detachable.
[0044] In addition, the electrochromic lens 300 may have one or more gripping portions, and in terms of maintaining a good balance while achieving a good design, it is preferable that the electrochromic lens 300 has two or more gripping portions, which are arranged in line-symmetric positions.
[0045] The electrochromic lens 300 preferably has second regions or gripping portions in the 1 to 3 o'clock and 9 to 11 o'clock directions 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 in use and is oriented vertically. 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 direction and the 10 o'clock direction as 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 upper side of the electrochromic lens 300 at the 1 o'clock direction and the 11 o'clock direction as 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 upper corners of the electrochromic lens 300 at the 2 o'clock direction and the 10 o'clock direction as viewed from the center of the electrochromic lens 300.
[0046] 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 shape), Wellington (an inverted trapezoid with the upper side longer than the lower side), oval (egg shape), square (approximately rectangular shape), and round (circular shape).
[0047] The electrochromic lens 300 that satisfies the above requirement a can be realized by selecting the sealing material that constitutes the sealing member 9, by improving the manufacturing method of the electrochromic sheet 100, by improving the trimming method of the base lens 30, etc.
[0048] <Components of electrochromic sheet> Hereinafter, each component of the electrochromic sheet 100 will be described in detail.
[0049] [Sealing material] The sealing material 8 integrally covers the side surface of the electrolyte layer 4 and the side surfaces of the first electrochromic layer 3 and the second electrochromic layer 5, and is used to prevent moisture and oxygen gas from entering the electrochromic element 10 from the outside, and to adhere to the first transparent substrate layer 1 and the second transparent substrate layer 7 to prevent peeling from the electrochromic element 10. In addition, if the first electrochromic layer 3 and the second electrochromic layer 5 formed between the opposing first electrode 2 and second electrode 6 are misaligned, the color development quality during operation will decrease, so the sealing material 8 is used to prevent this.
[0050] The average thickness (length in the stacking direction) of the sealing material 8 is adjusted according to the average thickness of the electrochromic elements 10, and is preferably set to about 20 μm or more and 100 μm or less, and more preferably about 40 μm or more and 80 μm or less, for example.
[0051] The sealing member 8 is formed using a sealing material described below.
[0052] (Sealing material) The sealing material in this embodiment is not particularly limited as long as it is an insulating material, but preferably contains a curable resin.
[0053] ·Curable resin The curable resin may be, for example, one or more selected from epoxy resin, acrylic resin, phenol resin, maleimide resin, silicone resin, urethane resin, cyanate resin, melamine resin, urea resin, and unsaturated polyester resin. Those having at least one of an ultraviolet reactive functional group and a heat reactive functional group are preferred, and those having a (meth)acryloyl group and / or an epoxy group are more preferred. The curable resin may, for example, be a thermosetting resin such as (meth)acrylate or epoxy resin.
[0054] 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.
[0055] 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.
[0056] The epoxy (meth)acrylate is not particularly limited, and examples thereof include those obtained by reacting an epoxy compound with (meth)acrylic acid in the presence of a basic catalyst according to a conventional method, etc. Examples thereof include epoxy (meth)acrylates derived from an epoxy resin such as a bisphenol A type epoxy resin or propylene glycol diglycidyl ether and (meth)acrylic acid.
[0057] 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.
[0058] Examples of the epoxy resin include novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins, bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, aromatic glycidylamine type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, and aminophenol type glycidylamine, hydroquinone type epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins, triphenolmethane type epoxy resins, triphenolpropane type epoxy resins, and alkyl glycidylamines. Examples of the epoxy resin include one or more selected from epoxy resins such as modified triphenolmethane type epoxy resins, triazine nucleus-containing epoxy resins, dicyclopentadiene modified phenol type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a phenylene and / or biphenylene skeleton, and naphthol aralkyl type epoxy resins having a phenylene and / or biphenylene skeleton; and aliphatic epoxy resins such as alicyclic epoxy resins such as vinylcyclohexene dioxide, dicyclopentadiene oxide, and alicyclic diepoxy adipide.
[0059] The sealing material of the present embodiment may further contain inorganic particles.
[0060] ·Inorganic particles Examples of inorganic particles include one or more types selected from silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, and the like.
[0061] The inorganic particles may be those whose surfaces have been hydrophobically treated. For example, the inorganic particles may be surface-treated by a known method using epoxysilane, aminosilane, (meth)acrylic silane, vinylsilane, methylchlorosilane, dimethylpolysiloxane, etc. The inorganic particles may be used in combination with those that have been hydrophobically treated and those that have not.
[0062] The content of the inorganic particles is from 1 to 80 mass %, preferably from 3 to 70 mass %, and more preferably from 20 to 60 mass %, based on the total amount of the sealing material.
[0063] ·others The sealing material of the present embodiment may contain organic particles, a polymerization initiator, a heat curing agent, and the like in addition to the above-mentioned curable resin and inorganic particles.
[0064] The organic particles may be, for example, one or more types selected from polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, silicone fine particles, core-shell type rubber fine particles, and the like.
[0065] Examples of the polymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.
[0066] Examples of the radical polymerization initiator include a photoradical polymerization initiator which generates radicals upon irradiation with light, and a thermal radical polymerization initiator which generates radicals upon heating.
[0067] 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.
[0068] Examples of the thermal radical polymerization initiator include those made of an azo compound, an organic peroxide, etc. Among them, a polymeric azo initiator made of a polymeric azo compound is preferred.
[0069] As the cationic polymerization initiator, a photocationic polymerization initiator can be suitably used. The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid upon irradiation with light, and may be either an ionic photoacid generating type or a nonionic photoacid generating type. Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts; and organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes.
[0070] The content of the polymerization initiator is preferably 0.1 to 30 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the polymerization initiator is equal to or more than the lower limit, the sealing material has better curability, whereas when the content of the polymerization initiator is equal to or less than the upper limit, the sealing material has better storage stability.
[0071] The heat curing agent is used to react and crosslink the heat-reactive functional groups in the curable resin by heating, and has the role of improving the adhesiveness and moisture resistance of the curable resin composition after curing. Examples of the heat curing agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, etc. Among these, solid organic acid hydrazides are preferably used.
[0072] The content of the above-mentioned heat curing agent is preferably 0.1 to 50 parts by weight, and more preferably 1 to 30 parts by weight, based on 100 parts by weight of the curable resin. When the content of the polymerization initiator is equal to or more than the lower limit, the sealing material has better curability, whereas when the content of the polymerization initiator is equal to or less than the upper limit, the sealing material has better coatability.
[0073] In addition, additives such as a silane coupling agent, a light blocking agent, a reactive diluent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other coupling agents may be contained as necessary.
[0074] (Method of manufacturing sealing materials) An example of a method for producing the sealing material of the present embodiment is a method in which a curable resin, inorganic particles, and additives such as a polymerization initiator and / or a heat curing agent or a silane coupling agent, which are added as necessary, are mixed using a mixer. Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, and a planetary mixer.
[0075] [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.
[0076] 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.
[0077] The electrolyte layer 4 includes a binder resin and an electrolyte.
[0078] The binder resin is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable that the binder resin contains a urethane resin unit in terms of the phase separation temperature and film strength as a polymer membrane. Also, by containing a polyethylene oxide (PEO) chain, the compatibility with the electrolyte is improved and the phase separation temperature can be increased. Also, by containing a polymethyl methacrylate (PMMA) chain, the compatibility with the electrolyte is improved and the phase separation temperature can be increased, similarly to the case of containing a PEO chain.
[0079] The electrolyte is not particularly limited, but examples thereof include inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids, and alkali supporting salts. Specific examples include LiClO4, LiBF4, LiAsF6, LiPF6, LiCF3SO3, LiCF3COO, KCl, NaClO3, NaCl, NaBF4, NaSCN, KBF4, Mg(ClO4)2, Mg(BF4)2, etc., and one or a combination of two or more of these can be used.
[0080] In addition, ionic liquids can also be used as electrolyte materials. Among these ionic liquids, organic ionic liquids are preferably used because they have a molecular structure that shows liquidity over a wide temperature range including room temperature and are easy to handle.
[0081] As the molecular structure of the organic ionic liquid, the cationic component may be, for example, an imidazole derivative such as N,N-dimethylimidazole salt, N,N-methylethylimidazole salt, or N,N-methylpropylimidazole salt; a pyridinium derivative such as N,N-dimethylpyridinium salt or N,N-methylpropylpyridinium salt; or an aliphatic quaternary ammonium derivative such as trimethylpropylammonium salt, trimethylhexylammonium salt, or triethylhexylammonium salt. In addition, it is preferable to use a fluorine-containing compound as the anionic component, taking into consideration stability in the atmosphere, such as BF4 - , CF3SO3 - , PF4 - , (CF3SO2)2N -etc.
[0082] Such an electrolyte material is preferably an ionic liquid containing any combination of cationic and anionic components.
[0083] 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.
[0084] Examples of the solvent include propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, polyethylene glycol, alcohols, and mixed solvents thereof.
[0085] The electrolyte filled as the electrolyte layer 4 may be either solid or liquid, but in addition to the electrolyte being a low-viscosity liquid, it may take various forms, such as a gel, a polymer cross-linked type, or a liquid crystal dispersion type. Of these, it is preferable that the electrolyte be formed into a gel or solid state. This can improve the element strength and reliability of the electrochromic element 10.
[0086] A preferred method for making the electrolyte layer 4 solid is, for example, a method in which a liquid containing an electrolyte and a solvent is held in a binder resin. This allows the electrolyte layer 4 to have both high ionic conductivity and solid strength. In addition, a photocurable resin is preferred as the polymer resin. This allows the electrolyte layer 4 to be solid at a lower temperature and in a shorter time than when the electrolyte layer 4 is solidified by thermal polymerization or evaporation of a solvent.
[0087] When the electrolyte layer 4 is in a gel state, it can be prepared, for example, as follows. First, a composition solution is prepared, and the prepared composition solution is sandwiched between a mold or a film and polymerized by a cast polymerization method or the like. The composition solution can be prepared by mixing an electrolyte solution obtained by mixing the ionic liquid or solid electrolyte with a solvent, a polymerizable material, a urethane acrylate monomer, and, if necessary, an acrylate monomer having a PEO chain, and, if necessary, an acrylate monomer having a PMMA chain in a desired ratio, and, if necessary, the polymerization initiator and other components can be mixed. As another preparation method, a method of applying a composition solution before polymerization onto one electrochromic layer and polymerizing it by ultraviolet irradiation or heating can be used. Also, a method of placing the supports on which the electrochromic layers have been formed facing each other with a gap of 5 μm to 150 μm maintained, filling the composition solution, and then polymerizing it by ultraviolet irradiation or heating can be used.
[0088] [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.
[0089] Below, we will explain the case where the second electrochromic layer 5 contains metal nanoparticles and an electrochromic material. Even if the first electrochromic layer 3 contains metal nanoparticles and an electrochromic material, the other configurations, effects, etc. are similar, although the oxidation-reduction action is different.
[0090] (Metal Nanoparticles) Metal nanoparticles have excellent electrical conductivity and can conduct electricity through electrochromic materials. The metal nanoparticles may be any conductive metal particles, and specifically, for example, one or more kinds selected from tin oxide, titanium oxide, zinc oxide, antimony (V) oxide, zirconium oxide, and yttrium oxide may be mentioned. Among them, tin oxide and titanium oxide are preferable.
[0091] The average primary particle diameter (hereinafter also referred to as "particle diameter") of the metal nanoparticles is preferably from 1 nm to 100 nm, and more preferably from 3 to 8 nm. By setting the particle size to the above lower limit or more, good color development and decolorization performance can be obtained. On the other hand, by setting the particle size to the above upper limit or less, the transparency of the second electrochromic layer 5 can be maintained, and the specific surface area can be increased, thereby increasing the amount of electrochromic material carried.
[0092] The electrochromic material carried by the metal nanoparticles may be one or more compounds.
[0093] The second electrochromic layer 5 is preferably formed from a sol solution of metal nanoparticles, which can provide a good haze value and increase the reflectance.
[0094] (Electrochromic Materials) The electrochromic material is composed of an electrochromic compound that undergoes an oxidation-reduction reaction when a voltage is applied, and can reversibly develop and decolorize.
[0095] 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.
[0096] The electrochromic material may be either an inorganic electrochromic compound or an organic electrochromic compound, or a conductive polymer known to exhibit electrochromism. The first electrochromic layer 3 and the second electrochromic layer 5 can be made of any of these electrochromic materials. However, when one of them is made of an electrochromic material having oxidative coloring properties, it is preferable that the other is made of an electrochromic material having reductive coloring properties. As the electrochromic material having oxidative coloring properties, a polymer obtained by polymerizing an oxidative coloring electrochromic composition containing a radical polymerizable compound is preferable, and an electrochromic composition containing a radical polymerizable compound having triarylamine is particularly preferable.
[0097] The length of a single molecule of the electrochromic material is preferably 5 nm or less.
[0098] (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.
[0099] 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.
[0100] The electrochromic material contained as the main material in the first electrochromic layer 3 and which exhibits color through an oxidation reaction is not particularly limited, and examples thereof include a polymer obtained by polymerizing a composition containing a radically polymerizable compound having a triarylamine, a bisacridan compound, a Prussian blue complex, and nickel oxide, and one or more of these may be used in combination.
[0101] Examples of polymers obtained by polymerizing a composition containing a radically polymerizable compound having a triarylamine include those described in JP-A-2022-25243, JP-A-2016-45464, and JP-A-2020-138925.
[0102] Furthermore, an example of a Prussian blue-type complex is a material made of Fe(III)4[Fe(II)(CN)6]3.
[0103] Among these, a polymer obtained by polymerizing a composition containing a radically polymerizable compound having triarylamine is preferably used, since it can be operated at a constant voltage, has excellent durability during repeated use, and can provide an electrochromic element with high contrast.
[0104] In addition, the composition containing the radical polymerizable compound having a triarylamine may contain another radical polymerizable compound different from the radical polymerizable compound having a triarylamine, and the polymer obtained by polymerizing such a composition may be composed of a crosslinked product in which these radical polymerizable compounds are crosslinked.
[0105] (Second Electrochromic Layer) The second electrochromic layer 5 contains, as a main material, an electrochromic material that changes from transparent to colored by a reduction reaction, and is thus a layer that is colored.
[0106] The average thickness of the second electrochromic layer 5 is not particularly limited, but is preferably about 0.2 μm to 5.0 μm, and more preferably about 1.0 μm to 4.0 μm. If the average thickness is less than 0.2 μm, it may be difficult to obtain a desired color density depending on the type of electrochromic material, and if it exceeds 5.0 μm, the manufacturing cost may increase and visibility may decrease due to coloring depending on the type of electrochromic material.
[0107] The second electrochromic layer 5 preferably uses an electrochromic material having the same color tone as the first electrochromic layer 3. This improves the maximum color density, and as a result, the contrast can be improved.
[0108] In contrast, when materials of different colors are used, color mixing becomes possible. In addition, by coloring the first electrode 2 and the second electrode 6 through oxidation and reduction reactions, the driving voltages in the electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 can be effectively reduced, and the repeated durability of the electrochromic sheet 100 can be improved.
[0109] The electrochromic material contained as the main material in the second electrochromic layer 5 and which exhibits coloration by a reduction reaction is not particularly limited, and examples thereof include inorganic electrochromic compounds, organic electrochromic compounds, conductive polymers, etc., and one or a combination of two or more of these can be used.
[0110] Examples of inorganic electrochromic compounds include tungsten oxide, molybdenum oxide, iridium oxide, titanium oxide, etc., and among these, tungsten oxide is preferred. Tungsten oxide is preferably used because it has a low color development / discoloration potential due to its low reduction potential, and is also excellent in durability because it is an inorganic material.
[0111] In addition, as the organic electrochromic compound, for example, azobenzene-based, anthraquinone-based, diarylethene-based, dihydroprene-based, dipyridine-based, styryl-based, styrylspiropyran-based, spirooxazine-based, spirothiopyran-based, thioindigo-based, tetrathiafulvalene-based, terephthalic acid-based, triphenylmethane-based, triphenylamine-based, naphthopyran-based, viologen-based, pyrazoline-based, phenazine-based, phenylenediamine-based, phenoxazine-based, phenothiazine-based, phthalocyanine-based, fluoran-based, fulgide-based, benzopyran-based, metallocene-based, and other low molecular weight organic electrochromic compounds can be mentioned, among which viologen-based compounds and dipyridine-based compounds are preferred.These compounds are preferably used because they have low color development and fading potential and show good color value.
[0112] Examples of viologen compounds include those described in JP 2022-025243 A, JP 3955641 A, JP 2007-171781 A, etc. Examples of dipyridine compounds include those described in JP 2007-171781 A, JP 2008-116718 A, etc.
[0113] Examples of the conductive polymer include polypyrrole, polythiophene, polyaniline, and derivatives thereof.
[0114] [Transparent base layer] The first transparent substrate layer 1 and the second transparent substrate layer 7 have the function of supporting the first electrode 2, the first electrochromic layer 3, the electrolyte layer 4, the second electrochromic layer 5, the second electrode 6, and the sealing material 8. They also serve as the outermost layers of the electrochromic sheet 100.
[0115] Furthermore, the first transparent substrate layer 1 and the second transparent substrate layer 7 constitute the outermost layers of the electrochromic sheet 100. That is, at least the first electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 are not exposed to the outside. Therefore, the first electrochromic layer 3, the electrolyte layer 4, and the second electrochromic layer 5 can be protected from moisture and oxygen gas from the outside, physical impacts, friction, and the like.
[0116] 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.
[0117] 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.
[0118] Among these, polycarbonate-based resins or polyamide-based resins are preferred, and polycarbonate-based resins are particularly preferred. Polycarbonate-based resins are rich in transparency (light transmissivity) and mechanical strength such as rigidity, and also have high heat resistance, so that the use of polycarbonate-based resins as the transparent resin can improve the transparency, impact resistance, and heat resistance of the first transparent substrate layer 1 and the second transparent substrate layer 7.
[0119] As the polycarbonate resin, various resins can be used, among which aromatic polycarbonate resins are preferable. Aromatic polycarbonate resins have aromatic rings in their main chains, which allows the first transparent substrate layer 1 and the second transparent substrate layer 7 to have superior strength.
[0120] 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.
[0121] Examples of bisphenols include bisphenol A and bisphenol (modified bisphenol) which is the source of the repeating unit of polycarbonate represented by the following formula (1A).
[0122] [ka]
[0123] (In formula (1A), X is an alkyl group having 1 to 18 carbon atoms, an aromatic group, or a cyclic aliphatic group; Ra and Rb are each independently an alkyl group having 1 to 12 carbon atoms; m and n are each an integer of 0 to 4; and p is the number of repeating units.)
[0124] Specific examples of bisphenols that are the source of the repeating units of the polycarbonate represented by formula (1A) include 4,4'-(pentane-2,2-diyl)diphenol, 4,4'-(pentane-3,3-diyl)diphenol, 4,4'-(butane-2,2-diyl)diphenol, 1,1'-(cyclohexanediyl)diphenol, 2-cyclohexyl-1,4-bis(4-hydroxyphenyl)benzene, 2,3-biscyclohexyl-1,4-bis(4-hydroxyphenyl)benzene, 1,1'-bis(4-hydroxy-3-methylphenyl)cyclohexane, and 2,2'-bis(4-hydroxy-3-methylphenyl)propane, and any of these may be used alone or in combination of two or more.
[0125] Among them, the polycarbonate resin is preferably a bisphenol-type polycarbonate resin having a skeleton derived from bisphenol as a main component. By using such a bisphenol-type polycarbonate resin, the first transparent substrate layer 1 and the second transparent substrate layer 7 exhibit even greater strength.
[0126] In this embodiment, the absorbance at a wavelength of 320 nm of the second transparent substrate layer 7 constituting the laminate A is preferably 1 or less, and more preferably 0.8 or less. The absorbance of the second transparent substrate layer 7 at a wavelength of 295 nm is preferably 1 or less, and more preferably 0.8 or less. In this embodiment, the second transparent substrate layer 7 constituting the laminate A may not contain an ultraviolet absorbing agent. In this case, an ultraviolet ray blocking function can be imparted to eyewear using the electrochromic sheet 100 of this embodiment. On the other hand, in this embodiment, the first transparent substrate layer 1 may contain a known ultraviolet absorbing agent.
[0127] Coloring agents As long as the first transparent substrate layer 1 and the second transparent substrate layer 7 have optical transparency, they may further contain a colorant, and the color may be any color, such as colorless, red, blue, yellow, etc.
[0128] These colors can be selected by incorporating a colorant such as a dye or a pigment in the first transparent substrate layer 1 and the second transparent substrate layer 7 . Examples of the dye include acid dyes, direct dyes, reactive dyes, and basic dyes, and one or more selected from these may be used in combination.
[0129] Specific examples of dyes include CI Acid Yellow 17, 23, 42, 44, 79, 142, CI Acid Red 52, 80, 82, 249, 254, 289, CI Acid Blue 9, 45, 249, CI Acid Black 1, 2, 24, 94, CI Food Black 1, 2, CI Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 14 4,173, CI Direct Red 1, 4, 9, 80, 81, 225, 227, CI Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, CI Direct Black 19, 38, 51, 71, 154, 168, 171, 195, CI Reactive Red 14, 32, 55, 79, 249, CI Reactive Black 3, 4, 35, etc.
[0130] The first transparent substrate layer 1 and the second transparent substrate layer 7 may contain, in addition to the transparent resin, dye or pigment described above, various additives such as antioxidants, fillers, plasticizers, light stabilizers, ultraviolet absorbers, heat absorbers, and flame retardants, as necessary.
[0131] Moreover, the first transparent substrate layer 1 and the second transparent substrate layer 7 may be either stretched or unstretched.
[0132] 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 to 1.8, more preferably 1.4 to 1.65. By setting the refractive index n1 of the first transparent substrate layer 1 and the second transparent substrate layer 7 within the above numerical range, the color developing and decoloring function of the electrochromic sheet 100 can be easily visually recognized.
[0133] The average thickness of the first transparent substrate layer 1 and the second transparent substrate layer 7 is preferably set to be 0.01 mm or more and 10.0 mm or less, more preferably 0.05 mm or more and 5.0 mm or less. By setting the average thickness of the first transparent substrate layer 1 and the second transparent substrate layer 7 within this range, it is possible to appropriately suppress or prevent the electrochromic sheet 100 from warping while making the electrochromic sheet 100 thinner.
[0134] The first transparent substrate layer and the second transparent substrate layer 7 may be made of the same or different materials. In addition, both may be stretched, or only one may be unstretched.
[0135] 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.
[0136] [electrode] The first electrode 2 and the second electrode 6 are electrodes that supply electrons between the first electrode 2 and the second electrode 6, or receive electrons from between the first electrode 2 and the second electrode 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 electrode 2 is provided on the surface of the first electrochromic layer 3 opposite to the electrolyte layer 4. The second electrode 6 is provided on the surface of the second electrochromic layer 5 opposite to the electrolyte layer 4.
[0137] The constituent material of the first electrode 2 and the second electrode 6 is not particularly limited as long as it is a transparent conductive material, and examples thereof include oxides such as ITO (indium tin oxide), FTO (F-doped tin oxide), ATO (antimony tin oxide), IZO (indium zinc oxide), In2O3, SnO2, Sb-containing SnO2, and Al-containing ZnO, Au, Pt, Ag, Cu, and alloys containing these, and one or more of these may be used in combination.
[0138] Examples of methods for producing the first electrode 2 and the second electrode 6 include vacuum deposition, sputtering, and ion plating. In addition, as long as the materials for the first electrode 2 and the second electrode 6 can be applied, various printing methods such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing can be used.
[0139] The average thickness of the first electrode 2 and the second electrode 6 is adjusted so as to obtain the electrical resistance value required for the oxidation-reduction reaction of the first electrochromic layer 3 and the second electrochromic layer 5. For example, when ITO is used as the constituent material of the first electrode 2 and the second electrode 6, the average thickness is preferably set to about 50 nm or more and 200 nm or less, more preferably about 100 nm or more and 150 nm or less, respectively.
[0140] Between each layer between the first electrode 2 and the second electrode 6, an intermediate layer such as an insulating porous layer or a protective layer may be provided.
[0141] [Columnar conductive part] The first columnar conductive portion 22 is provided as wiring so as to overlap, in a plan view, with the first electrode 2 extending from the electrochromic element 10 and penetrating the sealing material 8 (see FIG. 1). The first columnar conductive portion 22 is electrically connected to the first electrode 2 via the first auxiliary electrode layer 21.
[0142] The first columnar conductive portion 22 is exposed at an end of the eyeglass lens when the outer shape of the electrochromic sheet 100 is processed into the shape of an eyeglass lens in order to apply the electrochromic sheet 100 to the eyeglass lens. This allows electricity to be applied to the electrochromic element 10 from the outside via the first columnar conductive portion 22. The second columnar conductive portion 62, like the first columnar conductive portion 22, is exposed at the end of the eyeglass lens when the outer shape of the electrochromic sheet 100 is processed into the eyeglass lens shape in order to apply the electrochromic sheet 100 to the eyeglass lens. This allows electricity to be applied to the electrochromic element 10 from the outside via the second columnar conductive portion 62. In this case, the first columnar conductive portion 22 can be located on the bridge side of the eyeglass lens, and the second columnar conductive portion 62 can be located on the temple side (opposite the bridge side) of the eyeglass lens.
[0143] Furthermore, the first columnar conductive portion 22 and the second columnar conductive portion 62 each independently have an average thickness set to preferably about 10 μm or more and 100 μm or less, more preferably about 20 μm or more and 80 μm or less, and even more preferably about 30 μm or more and 70 μm or less.
[0144] The material for the first columnar conductive portion 22 and the second columnar conductive portion 62 may be a conductive paste having electrical conductivity. This can improve the adhesion between the first columnar conductive portion 22 and the second columnar conductive portion 62 and the sealing material 8.
[0145] (Other electrodes) The first auxiliary electrode layer 21 is provided as wiring by being laminated on the surface of the first electrode 2 opposite to the first transparent substrate layer 1 , and is electrically connected to the first columnar conductive portion 22 . Similarly, the second auxiliary electrode layer 61 is laminated as wiring on the surface of the second electrode 6 opposite the second transparent substrate layer 7, and is electrically connected to the second columnar conductive portion 62.
[0146] 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 electrode 2 and the second electrode 6, respectively. Therefore, by forming wiring electrically connected to the electrochromic element 10 with the laminate of the first electrode 2 and the first auxiliary electrode layer 21, and the laminate of the second electrode 6 and the second auxiliary electrode layer 61, respectively, it is possible to impart superior electrical conductivity to these wirings (laminates).
[0147] 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 electrode 2 and the second electrode 6, respectively, but materials with excellent conductivity are used, such as silver, aluminum, copper, chromium, and molybdenum, and one or a combination of two or more of these can be used.
[0148] The first auxiliary electrode layer 21 and the second auxiliary electrode layer 61 each have an average thickness preferably set to about 1 nm or more and 100 nm or less, more preferably about 5 nm or more and 50 nm or less, so that the first auxiliary electrode layer 21 and the second auxiliary electrode layer 61 can reliably function as auxiliary electrodes.
[0149] [Electrochromic sheet composition, thickness, etc.] The total thickness of the electrochromic sheet 100 of this embodiment is not particularly limited, but is preferably 0.3 mm or more and 10.0 mm or less, and more preferably 0.5 mm or more and 5.0 mm or less. By making the total thickness of the electrochromic sheet 100 equal to or greater than the above-mentioned lower limit, strength can be maintained, while by making the layer thickness equal to or less than the above-mentioned upper limit, the electrochromic sheet 100 can be easily processed, such as by cutting or bending.
[0150] Each layer of the electrochromic sheet 100 may be replaced with any layer having a similar function, or other layers may be further provided.
[0151] <Manufacturing method of electrochromic sheet> The method for producing the electrochromic sheet 100 includes the following steps. A step of forming a first electrode 2 on a first transparent substrate layer 1 and laminating a first electrochromic layer 3 on the first electrode 2; forming a second electrode 6 on a second transparent substrate layer 7, and forming a second electrochromic layer 5 on the second electrode 6; applying a sealing material onto the first electrode 2 so as to surround the outer edge of the first electrochromic layer 3, or applying a sealing material onto the second electrode 6 so as to surround the outer edge of the second electrochromic layer 5; a step of preparing an electrolyte layer 4, and bonding a first transparent substrate layer 1 and a second transparent substrate layer 2 together, with a first electrochromic layer 3 and a second electrochromic layer 5 facing each other with the electrolyte layer 4 interposed therebetween; curing the sealing material to form a sealing material 8; having In the lamination step, the sealing material is spread out, so that the first electrochromic layer 3 and the second electrochromic layer 5 are covered with the sealing material. In this way, the electrochromic sheet 100 is obtained.
[0152] <How to use electrochromic sheet> The method of using the electrochromic sheet 100 of this embodiment is as follows: A method of using an electrochromic sheet 100 comprising an electrochromic element 10, a sealant 8 covering a side surface of the electrochromic element 10, and a pair of transparent base layers sandwiching the electrochromic element 10 and the sealant 8, comprising the steps of: The method includes a step of processing the electrochromic sheet 100 into an electrochromic lens 300 that satisfies the following requirement b.
[0153] (Requirement b) The length of the inner edge of the sealant 8 measured in orthogonal projection when the sealant 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 sealant 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, 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, and S2 / S (percentage) is 1 to 40%, The second region is defined as a length of 4 mm at any position on the inner circumferential edge of the sealing material 8, 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), this includes the area where Wa (mm) is 1.5 mm or more.
[0154] The process of processing into electrochromic lens 300 can be performed by any known method, for example, by punching out electrochromic sheet 110 containing electrochromic elements 10 partitioned by sealing material 9 into the desired shape, or by further trimming the outer edge of plain lens 30 which contains electrochromic elements 10 punched out into the desired shape and has sealing material 9 on its outer edge.
[0155] Requirement b can be set and controlled in the same manner as requirement a above.
[0156] According to the method of 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.
[0157] <Electrochromic device> The electrochromic device of this embodiment has the above-mentioned electrochromic lens, and further has other means as necessary. The other means are not particularly limited and can be appropriately selected depending on the application. Examples of the other means include a power source, a fixing means, and a control means.
[0158] Although the embodiments of the present invention have been described above with reference to the drawings, these are merely examples of the present invention, and various configurations other than those described above can also be adopted. [Explanation of symbols]
[0159] 1 First transparent substrate layer 2 First electrode 3 First electrochromic layer 4 Electrolyte layer 5 Second Electrochromic Layer 6 Second electrode 7 Second transparent substrate layer 8. Encapsulating materials 10 Electrochromic elements 21 Auxiliary electrode layer 22 Columnar conductive part 30 Raw Lens 35 Resin layer 40 Mold 41 Upper mold 42 Lower mold 50 Protective Film 61 Auxiliary electrode layer 62 Columnar conductive part 70a Gripping part 70b Grip 70c grip part 100 Electrochromic Sheet 110 Electrochromic Sheet 120 Curved Sheet 210 Connecting sheet laminate 220 Curved element stack 250 Element Stack 300 Electrochromic Lenses
Claims
1. An electrochromic element; a sealing material that covers a side surface of the electrochromic element; a pair of transparent substrate layers sandwiching the electrochromic element and the sealing material; An electrochromic lens comprising: An electrochromic lens that satisfies the following requirement a. (Requirement a) 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, 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, and S2 / S (percentage) is 1 to 40%, 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. 2. The electrochromic lens of claim 1, The electrochromic lens has a through electrode that penetrates the sealing material in the second region.
3. 3. The electrochromic lens according to claim 1 or 2, The electrochromic lens has a gripping portion at the second region.
4. 3. The electrochromic lens according to claim 1 or 2, The electrochromic lens, wherein the sealing material is formed from a resin composition including a curable resin.
5. 3. The electrochromic lens according to claim 1 or 2, The electrochromic element is a solid or gel having a laminated structure in which an electrolyte layer and an electrochromic layer are laminated.
6. 6. The electrochromic lens of claim 5, The electrochromic lens, wherein the electrolyte layer is a solid or a gel.
7. 3. The electrochromic lens according to claim 1 or 2, The electrochromic lens further comprises an electrode layer between the transparent substrate layer and the electrochromic element.
8. 3. The electrochromic lens according to claim 1 or 2, The electrochromic lens, 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. 3. An electrochromic device using the electrochromic lens according to claim 1 or 2.
10. An electrochromic element; a sealing material that covers a side surface of the electrochromic element; a pair of transparent substrate layers sandwiching the electrochromic element and the sealing material; A method for using an electrochromic sheet, comprising: A method for using an electrochromic sheet, comprising the step of 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, 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, and S2 / S (percentage) is 1 to 40%, 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.
Citation Information
Patent Citations
Electrochromic composition and electrochromic element
CN108264893A
Electrochromic polymer and synthesis and uses thereof
CN110892001A
Electrochromic lens for improving color cast of polarized light reflector
CN111158200A
Electrochromic element
CN212623493U
Electrochromic device with a self-cleaning hydrophilic coating having a controlled surface morphology
JP2008541168A