JP7260046B1 - Electrochromic sheets, laminates, spectacle lenses and spectacles - Google Patents

Abstract

An electrochromic sheet capable of coloring and decoloring without delay is provided. The electrochromic device includes a first substrate, a second substrate, an electrochromic element, and a sealing portion, and the electrochromic element includes a first transparent electrode, a first auxiliary electrode, a second transparent electrode, and a second auxiliary electrode. An electrode and an electrochromic layer, wherein the first auxiliary electrode includes a strip-shaped first frame surrounding a portion of the electrochromic layer, and a first extraction portion projecting from the first frame to the outside of the colored region. and, the second auxiliary electrode has a strip-shaped second frame surrounding a portion of the electrochromic layer, and a second extraction portion projecting from the second frame to the outside of the colored region, Assuming the smallest imaginary rectangle among the rectangles circumscribing the colored region in plan view, the first extracting portion is provided on one end side in the direction of one side of the imaginary rectangle, and the second extracting portion is provided on the other end side. , the electrochromic sheet, wherein the first take-out portion and the second take-out portion are separated from each other by 40% or more of the length of one side thereof; [Selection drawing] Fig. 6

Description

The present invention relates to electrochromic sheets, laminates, spectacle lenses and spectacles.

Electrochromism is a phenomenon in which an oxidation-reduction reaction occurs when voltage is applied, resulting in a reversible color change. As an element utilizing such a phenomenon, an electrochromic element is known which uses a material exhibiting electrochromism and controls color by voltage application.

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

Electrochromic sheets having electrochromic elements are used as materials for eyewear such as sunglasses, for example.

JP 2017-167317 A

The transparent electrode used in the configuration of Patent Document 1 is formed using a material having high electrical conductivity and high visible light transmittance. Oxide such as ITO (Indium Tin Oxide) is known as a material for the transparent electrode.

On the other hand, the above materials have higher electrical resistance than metal materials. Therefore, in the electrochromic layer sandwiched between transparent electrodes made of ITO, there are areas where current is easily conducted and areas where it is difficult for current to be conducted.

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrochromic sheet capable of coloring and decoloring without delay. Another object of the present invention is to provide a laminate having such an electrochromic sheet, a spectacle lens, and spectacles having the spectacle lens.

In order to solve the above problems, the inventors investigated a configuration in which an auxiliary electrode that supplements the conductivity of the transparent electrode is also used. In general, the auxiliary electrode is formed using a metal material having lower electrical resistance than the material of the transparent electrode. By adopting a configuration using an auxiliary electrode, the problem of delay in discoloration can be solved.

On the other hand, in the study of the auxiliary electrode, it was found that depending on the shape of the auxiliary electrode to be formed, the function expected of the auxiliary electrode could not be fully exhibited, resulting in color unevenness. Based on such findings, the present invention was completed through intensive studies.

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

[1] A first substrate, a second substrate, an electrochromic element sandwiched between the first substrate and the second substrate, and an electrochromic element sandwiched between the first substrate and the second substrate, the first substrate and a sealing portion that partitions a colored region set between the second substrate and the electrochromic element, the electrochromic element comprising: a first transparent electrode provided on the first substrate side; A first auxiliary electrode arranged around and electrically connected to the first transparent electrode, a second transparent electrode provided on the second substrate side, and the second transparent electrode arranged around the colored region. and an electrochromic layer sandwiched between the first transparent electrode and the second transparent electrode, arranged in the colored region, and colored by voltage application. , the first auxiliary electrode has a strip-shaped first frame surrounding a portion of the electrochromic layer, and a first extraction portion projecting from the first frame to the outside of the colored region, The second auxiliary electrode has a strip-shaped second frame surrounding a portion of the electrochromic layer, and a second extraction portion protruding from the second frame to the outside of the colored region. Assuming a minimum virtual rectangle among the rectangles circumscribing the colored region, the first take-out portion is provided on one end side in the direction of one side of the virtual rectangle, and the second take-out portion is provided in the direction of the one side. The electrochromic sheet provided on the other end side of the electrochromic sheet, wherein the first take-out portion and the second take-out portion are separated from each other by 40% or more of the length of the one side in the direction of the one side.

[2] The first take-out portion is provided in a region extending from one end of the one side to 30% of the length, and the second take-out portion is provided in a region extending from the other end of the side to 30% of the length. The electrochromic sheet according to [1] provided in .

[3] The first extracting portion is provided in a region extending from the one end to 10% of the length, and the second extracting portion is provided in a region extending from the other end to 10% of the length. The electrochromic sheet according to [2].

[4] The first extractor and the second extractor are provided in a region from one end to the center of the virtual rectangle in a direction orthogonal to the one side of the virtual rectangle [1] to [3]. The electrochromic sheet according to any one of .

[5] The electrochromic layer includes a first electrochromic layer stacked on the first transparent electrode, a second electrochromic layer stacked on the second transparent electrode, the first electrochromic layer and the second electrochromic layer. and an electrolyte layer filled between the chromic layers, wherein the first electrochromic layer contains a material that exhibits coloration through an oxidation reaction, and the second electrochromic layer comprises a material that exhibits coloration through a reduction reaction. The electrochromic sheet according to any one of [1] to [4].

[6] A laminate comprising the electrochromic sheet according to any one of [1] to [5] and a lens material in which the electrochromic sheet is laminated.

[7] an electrochromic portion obtained by cutting the electrochromic sheet according to any one of [1] to [6] along the outer peripheries of the first auxiliary electrode and the second auxiliary electrode; and a lens body in which the electrochromic portion is laminated, wherein the lens body has a projecting portion having the same shape as the first extracting portion and the second extracting portion in a plan view.

[8] Spectacles comprising the spectacle lens according to [7] and a frame holding the spectacle lens, wherein the first extraction section and the second extraction section are electrically connected to the frame.

According to the present invention, it is possible to provide an electrochromic sheet capable of coloring and decoloring without delay. Further, it is possible to provide a laminate having such an electrochromic sheet, spectacle lenses, and spectacles having spectacle lenses.

FIG. 1 is a perspective view showing sunglasses using the electrochromic material of this embodiment. FIG. 2 is an exploded perspective view of the electrochromic sheet 150. FIG. 3 is a partial cross-sectional view taken along line III-III of FIG. 2. FIG. FIG. 4 is a partially enlarged view of the first auxiliary electrode 33. FIG. FIG. 5 is a partially enlarged view of the second auxiliary electrode 34. FIG. FIG. 6 is a plan view of the EC sheet 150. FIG. 7A and 7B are explanatory diagrams for explaining a lens manufacturing method using the EC sheet 150. FIG. FIG. 8 is an explanatory diagram showing the effect of the auxiliary electrode. FIG. 9 is an explanatory diagram showing the effect of the auxiliary electrode. FIG. 10 is an explanatory diagram showing the effect of the auxiliary electrode.

An electrochromic sheet, a laminate, a spectacle lens, and spectacles according to the present embodiment will be described below with reference to FIGS. 1 to 10. FIG. In addition, in all the drawings below, the dimensions and ratios of the constituent elements are appropriately changed in order to make the drawings easier to see. Also, in the following description, the term "electrochromic" may be abbreviated as "EC".

≪Glasses≫
FIG. 1 is a perspective view showing sunglasses (spectacles) using the electrochromic sheet (EC sheet) of this embodiment as a material. Sunglasses are an example of eyeglasses.

As shown in FIG. 1 , sunglasses 100 include a pair of lenses 110 (spectacle lenses) and a frame 120 .

[lens]
The lens 110 has visible light transmittance, and can reversibly develop and decolor by switching voltage application. In this specification, the term "lens (lens for spectacles)" includes both a lens having a light-collecting function and a lens not having a light-collecting function.

The lens 110 has an electrochromic portion 111 (EC portion 111) formed from an EC sheet, which will be described later, and a lens body 115 in which the EC portion 111 is laminated. When the user wears the sunglasses 100, the lens body 115 is positioned on the user side, and the EC portion 111 is positioned on the surface of the lens body 115 opposite to the user.

[flame]
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 user's head. The frame 120 positions the lenses 110 in front of the user's eyes.

Rim portion 121 is formed in a closed ring shape. A pair of rim portions 121 correspond to the user's right eye and left eye, respectively. Rim portion 121 may be an open ring. Also, the frame 120 may be configured without the rim portion 121 .

The bridge portion 122 connects the pair of rim portions 121 to each other. The bridge part 122 is positioned in front of the upper part of the user's nose when worn on the user's head.

The pair of temple portions 123 are connected to positions on the rim portion 121 opposite to the position to which the bridge portion 122 is connected. The temple part 123 is put on the user's ear when the user's head is worn.

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 wiring. The switch 125 can switch the application of the positive voltage, the application of the negative voltage, and the non-application of the voltage to the lens 110, for example.

A battery 126 is built in the temple portion 123 . Battery 126 is electrically connected to lens 110 via wiring.

The nose pad portion 124 is formed at a position corresponding to the user's nose on each rim portion 121 . The nose pad portion 124 contacts the user's nose. The nose pad portion 124 stabilizes the wearing state of the sunglasses 100 .

As a constituent material of the frame 120, for example, a metal material, a resin material, or the like can be used. Note that the shape of the frame 120 is not limited to the illustrated example as long as it is a shape that can be worn on the user's head.

≪Electrochromic sheet≫
2 is an exploded perspective view of the electrochromic sheet 150 (EC sheet 150), and FIG. 3 is a partial cross-sectional view taken along line III-III in FIG. The EC sheet 150 is used as a material for spectacle lenses, which will be described later.

As shown in FIGS. 2 and 3, the EC sheet 150 has a first substrate 11, a second substrate 12, an electrochromic element 30 (EC element 30), and a sealing portion . In FIG. 2, the sealing portion 40 is omitted.

The first substrate 11 and the second substrate 12 sandwich the EC element 30 and the sealing portion 40 . Also, the sealing part 40 is arranged around the EC element 30 between the first substrate 11 and the second substrate 12 to partition the first substrate 11 and the second substrate 12 . The area partitioned by the sealing portion 40 is a colored area AR whose color is changed by voltage application.

[First substrate, second substrate]
The first substrate 11 and the second substrate 12 are outermost layers of the EC sheet 150 . The first substrate 11 and the second substrate 12 are arranged facing each other and have a function as a protective layer that protects the EC element 30 and the like.

The first substrate 11 and the second substrate 12 are transparent to visible light. In this specification, having visible light transmittance may be referred to as “transparent”. Visible light transmittance is sometimes referred to as "transparency". As long as they have transparency, the first substrate and the second substrate 12 may be colorless or colored.

The first substrate 11 and the second substrate 12 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, and polyamide resins. Resins, cycloolefin-based resins, vinyl chloride-based resins, polyacetal-based resins, triacetyl cellulose (TAC), and the like.

As the material of the first substrate 11 and the second substrate 12, one of the above resins may be used, or two or more of them may be used in combination. As materials for the first substrate 11 and the second substrate 12, polycarbonate-based resins or polyamide-based resins are preferable.

Further, the materials of the first substrate 11 and the second substrate 12 may contain known fillers and additives as long as they have transparency. Also, the first substrate 11 and the second substrate 12 may be a single layer or a laminate.

The refractive index of the first substrate 11 and the second substrate 12 at a wavelength of 589 nm is preferably 1.3 or more and 1.8 or less, more preferably 1.4 or more and 1.65 or less. By setting the refractive indices of the first substrate 11 and the second substrate 12 within this range, the function of the electrochromic device 30 can be enhanced.

The average thickness of the first substrate 11 and the second substrate 12 is, for example, 0.05 mm or more and 10.0 mm or less, preferably 0.3 mm or more and 5.0 mm or less.

[Electrochromic element]
The EC element 30 undergoes discoloration (coloration, discoloration) due to electrochromism caused by voltage application. The EC element 30 has a first transparent electrode 31, a second transparent electrode 32, a first auxiliary electrode 33, a second auxiliary electrode 34, and an electrochromic layer 35 (EC layer 35).

(First transparent electrode, second transparent electrode)
The first transparent electrode 31 is provided on the first substrate 11 side of the EC element 30 and formed on the surface of the first substrate 11 on the second substrate 12 side. The second transparent electrode 32 is provided on the second substrate 12 side of the EC element 30 and formed on the surface of the second substrate 12 on the first substrate 11 side.

In FIG. 2, the first transparent electrode 31 has a protruding portion 31a at a position overlapping with a first extraction portion 332, which will be described later, similarly to the first extraction portion 332; good. Similarly, the second transparent electrode 32 also has a projecting portion 32a at a position that overlaps with a second extraction portion 342, which will be described later. However, this portion 32a may be omitted. .

The first transparent electrode 31 and the second transparent electrode 32 have transparency. Examples of materials for the first transparent electrode 31 and the second transparent electrode 32 include ITO, FTO (F-doped Tin Oxide), ATO (Antimony Tin Oxide), IZO (Indium Zinc Oxide), In ₂ O ₃ and SnO _{2 .} , Sb-containing SnO ₂ , Al-containing ZnO and other oxides, Au, Pt, Ag, Cu, and alloys containing these. As materials for the first transparent electrode 31 and the second transparent electrode 32, one of these may be used, or two or more of them may be used in combination.

The thicknesses of the first transparent electrode 31 and the second transparent electrode 32 are adjusted so as to ensure necessary transparency and obtain an electrical resistance value that allows appropriate voltage application to the EC layer 35 . When ITO is used as the material of 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, preferably 50 nm or more and 200 nm or less. is 50 nm or more and 150 nm or less, more preferably 60 nm or more and 130 nm or less.

(first auxiliary electrode, second auxiliary electrode)
The first auxiliary electrode 33 is arranged around the colored region AR in the peripheral portion of the first transparent electrode 31 and electrically connected to the first transparent electrode 31 . The first auxiliary electrode 33 has a strip-shaped first frame 331 and a first extraction portion 332 projecting from the first frame 331 to the outside of the colored region AR.

The first frame 331 surrounds part of the EC layer 35, that is, part of the colored region AR. Although the first frame 331 is curved in a plan view, it is not limited to this. The first frame 331 is provided at a position surrounding the lens 110 when the lens 110 is formed. The width of the first frame 331 is, for example, preferably 0.1 mm or more and 1.0 mm or less, more preferably 0.3 mm or more and 1.0 mm or less.

The first take-out portion 332 is provided at a position biased toward one end side of the first frame 331 from the center of the first frame 331 in plan view. The first extracting portion 332 is provided at a position near the bridge portion 122 or the temple portion 123 in the frame 120 when the lens 110 is formed.

As will be described later, when the EC sheet 150 is processed into the lens 110, a through hole 40a exposing the first extraction portion 332 is formed at a position overlapping the first extraction portion 332 in the sealing portion 40 in plan view. A conducting portion 51 is formed in the hole 40a. The first extracting portion 332 is used as a connecting portion with the conducting portion 51 . The formed conducting portion 51 is electrically connected to the first extraction portion 332 (the first auxiliary electrode 33).

The second auxiliary electrode 34 is arranged around the colored region AR on the peripheral surface of the second transparent electrode 32 and electrically connected to the second transparent electrode 32 . The second auxiliary electrode 34 has a strip-shaped second frame 341 and a second extraction portion 342 projecting from the second frame 341 to the outside of the colored region AR.

The second frame 341 surrounds part of the EC layer 35, that is, part of the colored region AR. Although the second frame 341 is curved in plan view, it is not limited thereto. The second frame 341 is provided at a position surrounding the lens 110 when the lens 110 is formed. The width of the second frame 341 is, for example, preferably 0.1 mm or more and 1.0 mm or less, more preferably 0.3 mm or more and 1.0 mm or less.

The second take-out portion 342 is provided at a position biased toward one end side of the second frame 341 from the center of the second frame 341 in plan view. The second extracting portion 342 is provided at a position near the bridge portion 122 or the temple portion 123 in the frame 120 when the lens 110 is formed.

Similarly, a through-hole exposing the second extraction portion 342 is formed at a position overlapping the second extraction portion 342 in the sealing portion 40, and a conducting portion is formed in the through-hole. The second extraction portion 342 is used as a connecting portion with the conducting portion. The formed conducting portion is electrically connected to the second extraction portion 342 (the second auxiliary electrode 34).

The first auxiliary electrode 33 and the second auxiliary electrode 34 do not overlap each other in plan view, and are located on opposite sides of the colored region AR in plan view. Also, the first lead-out portion 332 does not overlap the second transparent electrode 32 and the second lead-out portion 342 does not overlap the first transparent electrode 31 .

Assuming the smallest rectangle among the rectangles circumscribing the first transparent electrode 31 in a plan view, the first auxiliary electrode 33 of the EC sheet of the present embodiment is provided in a region on one end side in the direction of one side of the rectangle. , the second auxiliary electrode 34 is provided in a region on one end side in the direction of one side.
The length of the first auxiliary electrode 33 (first frame 331) in the side direction orthogonal to the direction of one side of the rectangle is 50% or more and 100% or less of the length of the first transparent electrode 31 in the orthogonal direction. is.
The length of the second auxiliary electrode 34 (second frame 341) in the orthogonal direction is 50% or more and 100% or less of the length of the second transparent electrode 32 in the orthogonal direction.

The electrical resistance value of the first auxiliary electrode 33 is lower than the electrical resistance value of the first transparent electrode 31 . Similarly, the electrical resistance value of the second auxiliary electrode 34 is lower than the electrical resistance value of the second transparent electrode 32 . Examples of constituent materials of the first auxiliary electrode 33 and the second auxiliary electrode 34 include silver, aluminum, copper, chromium, molybdenum, and the like. Conductive ink can also be used as a constituent material of the first auxiliary electrode 33 and the second auxiliary electrode 34 . As a constituent material of the first auxiliary electrode 33 and the second auxiliary electrode 34, one of these may be used, or two or more of them may be used in combination. The first auxiliary electrode 33 and the second auxiliary electrode 34 can be formed by sputtering, vapor deposition, or the like, for example. The first auxiliary electrode 33 and the second auxiliary electrode 34 can also be formed by printing using conductive ink.

The average thickness of the first auxiliary electrode 33 and the second auxiliary electrode 34 is preferably 1 nm or more and 100 nm or less. As for the average thickness of the 1st auxiliary electrode 33 and the 2nd auxiliary electrode 34, 5 nm or more and 50 nm or less are more preferable.

FIG. 4 is a partially enlarged view of the first auxiliary electrode 33. FIG. As shown in FIG. 5, in the first auxiliary electrode 33, the contour line of the connecting portion (represented by symbols A1 and A2 in FIG. 5) between the first frame 331 and the first extraction portion 332 is convex on the side of the colored region AR. is a curve that becomes The curvature radius of this curve is set to 40 mm or more. The radius of curvature can be measured and calculated by a known method.

Moreover, it is preferable that the width of the first extracting portion 332 directed outward from the first frame 331 is set to 10 mm or less.

The width of the first lead-out portion 332 is obtained by measuring the width W1 of the entire first auxiliary electrode 33 at the position where the first lead-out portion 332 is provided, and from the obtained width W1 of the first auxiliary electrode 33, 1 The width W2 of the frame 331 is excluded. A design value can be used for the width W2 of the first frame 331 if the design value is known. When the width of the first frame 331 is unknown, measure the width at a plurality of locations (for example, 5 locations at equal intervals) at equal intervals, and take the arithmetic mean value of the measured values as the width W2 of the first frame 331. can be done.

The width of the portion (tip portion) including at least the tip (one end) of the first frame 331 may be 0.1 mm or more and 1.0 mm or less. Since the width of the tip portion is 0.1 mm or more, the electric resistance can be lowered. Therefore, coloring and decoloring in the coloring area AR can be performed without delay. Since the width of the tip portion is 1.0 mm or less, it is difficult to visually recognize from the outside. Therefore, the first frame 331 is inconspicuous. Therefore, the aesthetic appearance of the sunglasses 100 can be enhanced. The width of the tip portion may be 0.3 mm or more and 1.0 mm or less.

FIG. 5 is a partially enlarged view of the second auxiliary electrode 34. FIG. Similarly to the first auxiliary electrode 33, in the second auxiliary electrode 34, the contour line of the connecting portion between the second frame 341 and the second extraction portion 342 (represented by symbols A3 and A4 in FIG. 6) is the colored area AR. It is a curve with a convex side. The radius of curvature of this curve is preferably set to 40 mm or more.

Moreover, it is preferable that the width of the second take-out portion 342 extending outward from the second frame 341 is set to 10 mm or less.

The width W2 is obtained by measuring the width W3 of the entire second auxiliary electrode 34 at the position where the second lead-out portion 342 is provided in the same manner as the width W1, and from the obtained width W3 of the second auxiliary electrode 34, It can be obtained as a value excluding the width W4 of the second frame 341 .

The width of the portion (tip portion) including at least the tip (one end) of the second frame 341 may be 0.1 mm or more and 1.0 mm or less. Since the width of the tip portion is 0.1 mm or more, the electric resistance can be lowered. Therefore, coloring and decoloring in the coloring area AR can be performed without delay. Since the width of the tip portion is 1.0 mm or less, it is difficult to visually recognize from the outside. Therefore, the second frame 341 is inconspicuous. Therefore, the aesthetic appearance of the sunglasses 100 can be enhanced. The width of the tip portion may be 0.3 mm or more and 1.0 mm or less.

FIG. 6 is a plan view of the EC sheet 150. FIG. As shown in FIG. 6, when assuming a minimum rectangle (virtual rectangle R) among the rectangles circumscribing the colored region AR in plan view, the first auxiliary electrode 33 is provided on one end side in the direction of one side of the virtual rectangle R. , and the second auxiliary electrode 34 is provided on one end side in the direction of one side. In FIG. 6, "one side of the virtual rectangle R" corresponds to the long side of the virtual rectangle R. As shown in FIG. That is, in FIG. 6, the "direction of one side" is the longitudinal direction of the imaginary rectangle R, and the "direction orthogonal to one side" is the lateral direction of the imaginary rectangle R. As shown in FIG.

It is preferable that the first extracting portion 332 is provided in an area AR1 extending from one end R1 of the imaginary rectangle R in the longitudinal direction LD to 30% of the length of the long side. Similarly, the second extractor 342 is preferably provided in an area AR2 extending from the other longitudinal end R2 of the imaginary rectangle R to 30% of the length of the long side. That is, the first take-out portion 332 and the second take-out portion 342 are provided at positions separated by 0.4 L or more, where L is the length of one side of the imaginary rectangle R (here, the length in the longitudinal direction). there is The first extraction portion 332 and the second extraction portion 342 are preferably provided at positions separated by 0.6L or more, and more preferably provided at positions separated by 0.8L or more.

Further, it is preferable that the region AR1 is a region extending from one end R1 to 10% of the length of the long side, and the region AR2 is a region extending from the other end R2 to 10% of the length of the long side.

Furthermore, the first extracting portion 332 and the second extracting portion 342 are provided in a region from one end of the imaginary rectangle R in the transverse direction SD to the center (50% of the entire transverse direction) of the transverse direction SD. and preferred. It is more preferable that the first take-out portion 332 and the second take-out portion 342 are provided in a region extending from 20% to 50% of the entire widthwise direction from one end of the imaginary rectangle R in the widthwise direction SD.

(electrochromic layer)
As shown in FIGS. 2 and 3, the EC layer 35 includes a first electrochromic layer 351 (first EC layer 351) laminated on the first transparent electrode 31 and a second electrochromic layer 352 laminated on the second transparent electrode 32. (second EC layer 352 ) and an electrolyte layer 353 filled between the first EC layer 351 and the second EC layer 352 .

(First electrochromic layer)
The first EC layer 351 is a layer whose color changes, and contains as a main material a material that is colored by an oxidation reaction. Materials that are colored by an oxidation reaction include, for example, polymers of radically polymerizable compounds having a triarylamine structure, bisacridane compounds, triphenylamine, benzidine, Prussian blue-type complexes, nickel oxide, and the like, exhibiting electrochromism, and EC. Known materials used for devices can be mentioned.

Polymers of radically polymerizable compounds having a triarylamine structure include, for example, those described in JP-A-2016-45464, JP-A-2020-138925, and the like.

As a 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.

The average thickness of the first EC layer 351 is preferably 0.1 μm or more and 30 μm or less. More preferably, the average thickness of the first EC layer 351 is 0.4 μm or more and 10 μm or less.

(Second electrochromic layer)
The second EC layer 352 is a layer that changes color, and contains as a main material a material that is colored by a reduction reaction. Examples of materials that are colored by a reduction reaction include inorganic electrochromic compounds such as tungsten oxide, molybdenum oxide, iridium oxide, and titanium oxide; organic electrochromic compounds such as viologen-based compounds and dipyridine-based compounds; Known materials used for devices can be mentioned.

As a 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.

The color (color 1) that the first EC layer 351 is colored by the oxidation reaction and the color (color 2) that the second EC layer 352 is colored by the reduction reaction may be the same color tone or different color tones. . When color 1 and color 2 have the same color tone, the maximum color density can be increased and the contrast can be improved. When the color 1 and the color 2 are different tones, the coloring of the EC element 30 is the color after the color 1 and the color 2 are mixed.

By coloring both the first EC layer 351 and the second EC layer 352, the redox pigments of the first EC layer 351 and the second EC layer 352 can be colored at the same time. Therefore, the coloring speed can be improved.

The average thickness of the second EC layer 352 is preferably 0.2 μm or more and 5.0 μm or less. More preferably, the average thickness of the second EC layer 352 is 1.0 μm or more and 4.0 μm or less. When the average thickness of the second EC layer 352 is 0.2 μm or more, the color density can be increased. If the average thickness of the second EC layer 352 is 5.0 μm or less, manufacturing costs can be suppressed. When the average thickness of the second EC layer 352 is 5.0 μm or less, visibility is less likely to be lowered due to coloring.

(Electrolyte layer)
An 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 ionic conductivity.

Examples of the electrolyte include inorganic ion salts such as alkali metal salts and alkaline earth metal salts; supporting salts such as quaternary ammonium salts, acids and alkalis. Electrolyte counterions (anions) include halogen, thiocyanate (SCN ⁻ ), chlorate (ClO ₃ ⁻ ), perchlorate (ClO ₄ ⁻ ), tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ), trifluoromethanesulfonate ion (CF ₃ SO ₃ ⁻ ), trifluoroacetate ion (CF ₃ COO ⁻ ), bisfluorosulfoniumimide (N(SO ₂ F) ₂ ⁻ ) can be mentioned.

Specific examples of such electrolytes include LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg(ClO ₄ ) ₂ , Mg(BF ₄ ) ₂ and the like. As the electrolyte, one of these may be used, or two or more of them may be used in combination.

An ionic liquid can also be used as the electrolyte material. Among ionic liquids, organic ionic liquids are easy to handle because they have molecular structures that remain liquid over a wide temperature range including room temperature.

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

[Sealing part]
The sealing portion 40 is arranged between the first substrate 11 and the second substrate 12 and partitions the coloring area AR. The material of the sealing portion 40 is not particularly limited as long as it is a transparent insulating material. Examples of materials for the sealing portion 40 include resin materials such as acrylic resin and epoxy resin; inorganic oxides such as silicon oxide (SiO ₂ ), silicon oxynitride (SiON), and aluminum oxide (Al ₂ O ₃ ); things, etc.

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.

≪Laminates, eyeglass lenses≫
7A and 7B are explanatory diagrams for explaining a lens manufacturing method using the EC sheet 150. FIG.

First, as shown in FIG. 7A, the EC sheet 150 is subjected to a bending process under heating so that the EC sheet 150 is curved according to the curvature of the intended lens. Bending is performed by, for example, press molding or vacuum molding.

Next, as shown in FIG. 7B, the curved EC sheet 150 is insert-molded as an insert product, and the 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" in the present invention. The lens material 119 becomes the lens main body 115 by performing processing described later.

The lens material 119 has visible light transparency. As the material of the lens member 119, a thermoplastic resin known as a material for optical members can be used.

If the material of the lens material 119 is the same as or the same as the main material of the substrate (the first substrate 11 or the second substrate 12) in contact with the lens material 119 in the EC sheet 150, the EC sheet 150 and the lens material 119 are brought into close contact with each other. Easy and preferred. Further, if the material of the substrate and the material of the lens material 119 are the same or the same, the difference in refractive index between the substrate and the lens material 119 can be reduced, and the light at the interface between the EC sheet 150 and the lens material 119 can be reduced. Scattering and reflection can be suppressed. The refractive index difference between the substrate and the lens material 119 is preferably 0.2 or less, more preferably 0.1 or less.

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

Next, surface polishing of the lens material 119, hard coating treatment of the surfaces of the EC sheet 150 and the lens material 119, and antireflection treatment are performed. After that, a through hole is formed in the sealing portion 40 at a position overlapping the first extraction portion 332 and the second extraction portion 342, and a conducting portion is formed in the through hole.

The conductive portion can be formed by a conductive paste filled inside the through-hole and a conductive tubular member inserted inside the through-hole. In addition, as long as it is formed in the through-hole 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), a known material is appropriately applied. can do.

Next, as shown in FIG. 7C, the laminate 160 is trimmed to have a shape corresponding to the rim portion 121 of the sunglasses 100 described above. At this time, the trimming around the first take-out portion 332 and the second take-out portion 342 is performed using, for example, a rotating cylindrical grindstone G. As shown in FIG.

An EC portion 111 obtained by cutting the EC sheet 150 along the outer periphery of the first auxiliary electrode 33 and the second auxiliary electrode 34 by such processing, and a lens body 115 in which the EC portion 111 is laminated are provided. A lens 110 is obtained (see FIG. 1). The obtained lens 110 corresponds to the "spectacle lens" in the present invention.

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 protruding portion 115a having the same shape as the first extracting portion 332 and the second extracting portion 342 in plan view.

The resulting lens 110 is assembled with the frame 120 shown in FIG. At that time, the first extracting portion 332 and the second extracting portion 342 of the EC portion 111 are electrically connected to the frame 120 via respective conducting portions. 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. .
Sunglasses 100 are thus obtained.

According to the EC sheet 150 configured as described above, the following effects are obtained.

8 to 10 are explanatory diagrams showing the effect of the auxiliary electrodes (first auxiliary electrode, second auxiliary electrode). FIG. 8 shows the EC part of a spectacle lens manufactured by the above method using an EC sheet having no auxiliary electrodes. FIG. 9 shows an EC portion of a spectacle lens manufactured by the above method using an EC sheet having auxiliary electrodes in which extraction portions are close to each other. FIG. 10 shows an EC portion (EC portion 111) of a spectacle lens manufactured by the method using the EC sheet 150 described above.

First, in the EC part 111X shown in FIG. , a current directly flows from the first conductive portion 51 and the second conductive portion 52 to the transparent electrode.

At this time, in the shortest path (indicated by symbol D1) connecting the first conductive portion 51 and the second conductive portion 52, the path is short and the electrical resistance is small, so that the current flows easily. A path (indicated by symbol D2) connecting the portion 52 by detouring is less likely to allow current to flow than the path D1. As a result, in the colored area AR, a region distant from the first conductive portion 51 and the second conductive portion 52, which overlaps with the path D2, is more likely to cause delay in discoloration than the area overlapping with the path D1.

Also, as in the EC portion 111Y shown in FIG. 9, in the EC sheet which is the material, when the extraction portions of the auxiliary electrodes are not provided apart from each other by 40% or more of the length in the longitudinal direction of the imaginary rectangle R but are close to each other. , works as follows.

When a battery is connected to the conductive portions 51 and 52 provided in each lead-out portion and voltage is applied, the first auxiliary electrode 33Y conducts electricity from the first lead-out portion 332Y to the first frame body 331Y, thereby Electricity is applied to the first transparent electrode 31 from the body 331Y. Further, in the second auxiliary electrode 34Y, electricity is applied from the second extracting portion 342Y to the second frame 341Y, and electricity is applied to the second transparent electrode 32 from the second frame 341Y. Such a current is designated Y1.

On the other hand, in the first auxiliary electrode 33Y, the first transparent electrode 31 is also energized from the first frame 331Y in the vicinity of the first extraction portion 332Y. Similarly, in the second auxiliary electrode 34Y, the second transparent electrode 32 is also energized from the second frame 341Y in the vicinity of the second extraction portion 342Y. Such a current is designated Y2.

In the EC portion 111Y, the current Y1 flows more easily than the current Y2 because the extraction portions are close to each other. As a result, in the colored region AR, the color change due to the current Y1 is dominant, and the color change due to the current Y2 tends to be delayed.

On the other hand, as in the EC part 111 shown in FIG. In the longitudinal direction, when they are provided at a distance of 40% or more of the length of the long side, they operate as follows.

In the first auxiliary electrode 33 , when a voltage is applied to the first lead-out portion 332 via the conductive portion 51 , the first lead-out portion 332 is energized toward the first frame 331 , and then the first auxiliary electrode 33 is energized. Electricity is applied from the electrode 33 to the first transparent electrode 31 . Such a current is designated C1.

Similarly, in the second auxiliary electrode 34 , when a voltage is applied from the external power source to the second lead-out portion 342 via the second conducting portion 52 , first, the voltage is applied from the second lead-out portion 342 toward the second frame 341 . Electricity is applied, and then electricity is applied from the second auxiliary electrode 34 to the second transparent electrode 32 . Such a current is designated C2.

In the EC section 111, the extraction sections are appropriately separated from each other, so that the current C1 and the current C2 tend to flow equally. As a result, in the colored region AR, a delay between the discoloration by the current C1 and the discoloration by the current C2 is unlikely to occur.

At this time, the first auxiliary electrode 33 covers most of the widthwise direction of one end of the first transparent electrode 31, and the second auxiliary electrode 34 covers most of the widthwise direction of the other end of the second transparent electrode 32. covering. Therefore, in the EC portion 111, when a voltage is applied, the timing of energization can be easily aligned in the entire colored region AR via the auxiliary electrode, and delay in discoloration can be suppressed.

Also, the first auxiliary electrode 33 and the second auxiliary electrode 34 are provided in the peripheral portion of the colored area AR and are not present in the center of the colored area AR. Therefore, it does not interfere with the coloring of the coloring area AR.

According to the electrochromic sheet having the above-described structure, the presence of the first auxiliary electrode 33 and the second auxiliary electrode 34 enables coloring and decoloring to be performed without delay.

Further, according to the laminate, spectacle lens, and spectacles configured as described above, by having the electrochromic sheet, it is possible to perform color development and decoloration without delay.

In this embodiment, the sunglasses 100 are shown as an example of spectacles, but the spectacles are not limited to this. The lens 110 may be applied to, for example, goggles for protecting the eyes from wind and rain, dust, chemicals, and the like.

Further, in the present embodiment, the EC layer 35 has the first EC layer 351 and the second EC layer 352, but the present invention is not limited to this. Even if the EC layer 35 has only one of the first EC layer 351 and the second EC layer 352, the effects of the present invention can be obtained.

Although the preferred embodiments according to the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to such examples. The various shapes, combinations, and the like of the constituent members shown in the above examples are merely examples, and can be variously changed based on design, specifications, etc., without departing from the gist of the present invention.

Reference Signs List 11 First substrate 12 Second 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) 40... Sealing part 110... Lens 111... Electrochromic part (EC part) 115... Lens main body 119... Lens material 120... Frame 122... Bridge part 123 ...Temple part 150...Electrochromic sheet (EC sheet) 160...Laminated body 331...First frame 332...First extraction part 341...Second frame 342...Second extraction part 351...Second extraction part 1 electrochromic layer (first EC layer), 352... second electrochromic layer (second EC layer), 353... electrolyte layer, AR... colored region

Claims (9)

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 electrochromic element includes a first transparent electrode provided on the first substrate side,
a first auxiliary electrode disposed around the colored region and electrically connected to the first transparent electrode;
a second transparent electrode provided on the second substrate side;
a second auxiliary electrode disposed around the colored region and electrically connected to the second transparent electrode;
an electrochromic layer sandwiched between the first transparent electrode and the second transparent electrode, disposed in the colored region, and colored by voltage application;
The first auxiliary electrode includes a strip-shaped first frame surrounding part of the electrochromic layer;
a first extraction portion projecting from the first frame to the outside of the colored region;
The second auxiliary electrode includes a strip-shaped second frame surrounding a portion of the electrochromic layer;
a second extraction portion projecting from the second frame to the outside of the colored region;
The first extracting portion planarly overlaps the sealing portion and has a width of 10 mm or less,
The second extracting portion planarly overlaps the sealing portion and has a width of 10 mm or less,
Assuming the smallest imaginary rectangle among the rectangles circumscribing the colored region in plan view,
The first extractor is provided on one end side of the virtual rectangle in the direction of one side,
The second extraction part is provided on the other end side in the direction of the one side,
The electrochromic sheet, wherein the first take-out part and the second take-out part are separated from each other by 40% or more of the length of the one side in the direction of the one side. The first extraction part is provided in a region from one end of the one side to 30% of the length,
2. The electrochromic sheet according to claim 1, wherein said second take-out portion is provided in a region extending from the other end of said one side to 30% of said length. The first extraction part is provided in a region from the one end to 10% of the length,
3. The electrochromic sheet according to claim 2, wherein said second extraction portion is provided in a region extending from said other end to 10% of said length. 2. The electrochromic sheet according to claim 1, wherein said first take-out portion and said second take-out portion are provided in a region from one end to the center of said imaginary rectangle in a direction orthogonal to said one side of said imaginary rectangle. The electrochromic layer includes a first electrochromic layer laminated on the first transparent electrode;
a second electrochromic layer laminated on the second transparent electrode;
an electrolyte layer filled between the first electrochromic layer and the second electrochromic layer;
The first electrochromic layer contains a material that exhibits coloring due to an oxidation reaction,
2. The electrochromic sheet according to claim 1, wherein the second electrochromic layer contains a material that is colored by a reduction reaction. an electrochromic sheet according to claim 1;
and a lens material in which the electrochromic sheet is laminated. an electrochromic portion obtained by cutting the electrochromic sheet according to claim 1 along the outer peripheries of the first auxiliary electrode and the second auxiliary electrode;
a lens body in which the electrochromic portion is laminated,
The spectacle lens, wherein the lens body has a protruding portion having the same shape as the first extracting portion and the second extracting portion in a plan view. an electrochromic portion obtained by cutting an electrochromic sheet;
a lens body in which the electrochromic portion is laminated,
The electrochromic sheet comprises 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 electrochromic element includes a first transparent electrode provided on the first substrate side,
a first auxiliary electrode disposed around the colored region and electrically connected to the first transparent electrode;
a second transparent electrode provided on the second substrate side;
a second auxiliary electrode disposed around the colored region and electrically connected to the second transparent electrode;
an electrochromic layer sandwiched between the first transparent electrode and the second transparent electrode, disposed in the colored region, and colored by voltage application;
The first auxiliary electrode includes a strip-shaped first frame surrounding part of the electrochromic layer;
a first extraction portion projecting from the first frame to the outside of the colored region;
The second auxiliary electrode includes a strip-shaped second frame surrounding a portion of the electrochromic layer;
a second extraction portion projecting from the second frame to the outside of the colored region;
Assuming the smallest imaginary rectangle among the rectangles circumscribing the colored region in plan view,
The first extractor is provided on one end side of the virtual rectangle in the direction of one side,
The second extracting portion is provided on the other end side in the direction of the one side,
The first extraction part and the second extraction part are provided apart from each other by 40% or more of the length of the one side in the direction of the one side,
The electrochromic portion is obtained by cutting the electrochromic sheet along the outer peripheries of the first auxiliary electrode and the second auxiliary electrode,
The spectacle lens, wherein the lens body has a protruding portion having the same shape as the first extracting portion and the second extracting portion in a plan view. A spectacle lens according to claim 7 or 8 ;
a frame that holds the spectacle lens,
The first extraction part and the second extraction part are spectacles electrically connected to the frame.

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