KR102777109B1 - Electrochromic device and windows apparatus having the same - Google Patents

Abstract

The embodiment provides an electrochromic element including a first substrate; a second substrate disposed on the first substrate; and an electrochromic member disposed between the first substrate and the second substrate, and having a light transmittance change rate of less than 0.25 measured by the following measuring method.

Description

{Electrochromic device and windows apparatus having the same}

The present invention relates to an electrochromic device and a window device including the same.

Electrochromic films are films that change color by undergoing redox reactions at each oxidation electrode and reduction electrode depending on an applied potential, and are films that can be artificially controlled by the user to provide visible light and infrared rays, and various types of inorganic oxides are used as electrode materials.

As described above, various electrochromic films have been developed and patented. Looking at the contents of the patent applications, Korean Patent Publication No. 2001-0087586 discloses a film in which MoO3, a reduced chromogenic oxide, is deposited on one of two ITO films (1A, 1B) in which an indium-tin oxide thin film having conductivity is deposited on a glass film, and WO3, a reduced chromogenic material, is deposited on the other, and then a solid electrolyte of lithium, an alkali metal, is deposited thereon, and polyaniline, a conductive polymer, is placed between the two films and passed through a high-frequency compression roller to apply voltage, thereby changing the color of the film from transparent to blue. Korean Utility Model Publication No. 0184841 discloses a film in which indium-tinoxide is deposited on a 0.05 mm thick glass film, and then WO3, a reduced chromogenic material, and IrO2, an oxidized chromogenic material, are deposited between an α-PEO copolymer, a polymer solid electrolyte. A color-changing film induced by electric energy is known, characterized by being bonded to both sides of a transition metal oxide film by a high-frequency roller.

The present invention seeks to provide an electrochromic device having improved durability and a window device including the same.

An electrochromic element according to an embodiment includes a first substrate; a second substrate disposed on the first substrate; and an electrochromic member disposed between the first substrate and the second substrate; and a light transmittance change rate measured by the following measurement method 1 may be less than 0.25.

[Measurement Method 1]

Through the first substrate, the electrochromic part is irradiated with ultraviolet light from a UVA 340 ultraviolet lamp at an intensity of 7.5 W/㎡ for 1 hour, the first light transmittance of the electrochromic element is measured before the irradiation with the ultraviolet light, the second light transmittance of the electrochromic element is measured after the irradiation with the ultraviolet light, and the light transmittance change rate is a value obtained by dividing the difference between the first light transmittance and the second light transmittance by the first light transmittance.

In an electrochromic device according to one embodiment, a haze change measured by the following measurement method 2 may be less than 5.5%.

[Measurement Method 2]

Before the ultraviolet irradiation, the first haze of the electrochromic element according to the embodiment is measured, and after the ultraviolet irradiation, the second haze of the electrochromic element according to the embodiment is measured, and the haze change is a value obtained by subtracting the first haze from the second haze.

In an electrochromic device according to one embodiment, the L* change measured by the measurement method 3 described below may be less than 9.

[Measurement Method 3]

Before the ultraviolet irradiation, the first L* of the electrochromic element is measured, and after the ultraviolet irradiation, the second L* of the electrochromic element is measured, and the change in L* is the absolute value of the value obtained by subtracting the first L* from the second L*.

In an electrochromic device according to one embodiment, the a* change measured by the following measuring method 4 may be less than 5.

[Measurement Method 4]

Before the ultraviolet irradiation, the first a* of the electrochromic element is measured, and after the ultraviolet irradiation, the second a* of the electrochromic element is measured, and the change in a* is the absolute value of the value obtained by subtracting the first a* from the second a*.

In an electrochromic device according to one embodiment, the b* change measured by the following measuring method 5 may be less than 10.

[Measurement Method 5]

Before the ultraviolet irradiation, the first b* of the electrochromic element is measured, and after the ultraviolet irradiation, the second b* of the electrochromic element is measured, and the change in b* is the absolute value of the value obtained by subtracting the first b* from the second b*.

In one embodiment, the first substrate comprises an ultraviolet ray blocking layer, and the ultraviolet ray blocking layer can have a transmittance of 10% or less for ultraviolet rays of 340 nm.

In one embodiment, the UV-blocking layer may include at least one UV absorbent selected from the group consisting of a benzophenone-based UV absorbent, a benzoxazinone-based UV absorbent, a benzotriazole-based UV absorbent, or a triazine-based UV absorbent.

In one embodiment, the first light transmittance may be from 50% to 85%, and the first haze may be from 0.1% to 5%.

In an electrochromic device according to one embodiment, the first L* may be 80 to 100, the first a* may be -2 to 1.5, and the first b* may be 0.5 to 4.

In one embodiment, the ultraviolet ray blocking layer can be disposed between the first substrate and the electrochromic portion.

A frame according to an embodiment; a window mounted on the frame; and an electrochromic element disposed on the window, wherein the electrochromic element comprises: a first substrate; a second substrate disposed on the first substrate; and an electrochromic section disposed between the first substrate and the second substrate, wherein a light transmittance change rate measured by the following measuring method 1 may be less than 0.25.

[Measurement Method 1]

Through the first substrate, the electrochromic part is irradiated with ultraviolet light from a UVA 340 ultraviolet lamp at an intensity of 7.5 W/㎡ for 1 hour, the first light transmittance of the electrochromic element is measured before the irradiation with the ultraviolet light, the second light transmittance of the electrochromic element is measured after the irradiation with the ultraviolet light, and the light transmittance change rate is a value obtained by dividing the difference between the first light transmittance and the second light transmittance by the first light transmittance.

Since the electrochromic element according to the embodiment effectively blocks external ultraviolet rays, the internal electrochromic part can be effectively protected from external ultraviolet rays.

Accordingly, the electrochromic element according to the embodiment can prevent electrons from being generated in the first discoloration layer when external ultraviolet rays are incident. Accordingly, the electrochromic element according to the embodiment can prevent some discoloration due to external ultraviolet rays.

Therefore, the electrochromic element according to the embodiment can have uniform optical characteristics regardless of external environments such as ultraviolet rays contained in sunlight.

Accordingly, the electrochromic element according to the embodiment is driven to have constant optical characteristics. In addition, since the electrochromic element according to the embodiment has constant driving characteristics, it can be driven with a constant driving voltage.

Accordingly, the electrochromic element according to the embodiment can be driven with a constant driving voltage and thus can have improved durability.

FIG. 1 is a cross-sectional view illustrating one section of an electrochromic device according to an embodiment.
FIG. 2 is a cross-sectional view illustrating an electrochromic element according to another embodiment.
Figures 3 to 6 are drawings illustrating a process for manufacturing an electrochromic element according to an embodiment.
Figure 7 is a diagram showing an example of the spectrum of light emitted by a UVA 340 lamp.
FIG. 8 is a drawing illustrating a window device according to an embodiment.

In the description of embodiments, when each part, surface, layer or substrate is described as being formed "on" or "under" each part, surface, layer or substrate, "on" and "under" include both being formed "directly" or "indirectly" via another component. In addition, the reference for on or under each component is described with reference to the drawings. The size of each component in the drawings may be exaggerated for the purpose of description and does not mean the size actually applied.

FIG. 1 is a cross-sectional view illustrating one section of an electrochromic device according to an embodiment.

Referring to FIG. 1, an electrochromic element according to an embodiment includes a first substrate (100), a second substrate (200), an ultraviolet ray blocking layer (800), and an electrochromic portion (11).

The above-mentioned electrochromic part (11) includes a first transparent electrode (300), a second transparent electrode (400), a first chromic layer (500), a second chromic layer (600), and an electrolyte layer (700).

The above first substrate (100) supports the ultraviolet ray blocking layer (800) and the electrochromic portion (11) together with the above second substrate (200).

The first substrate (100) supports, together with the second substrate (200), the first transparent electrode (300), the first discoloration layer (500), the second discoloration layer (600), the second transparent electrode (400), and the electrolyte layer (700).

In addition, the first substrate (100) sandwiches the first transparent electrode (300), the first discoloration layer (500), the second discoloration layer (600), the second transparent electrode (400), and the electrolyte layer (700) together with the second substrate (200). The first substrate (100) can protect the first transparent electrode (300), the first discoloration layer (500), the second discoloration layer (600), the second transparent electrode (400), and the electrolyte layer (700) together with the second substrate (200) from external physical impact and chemical impact.

The first substrate (100) may include a polymer resin. The first substrate (100) may include at least one selected from the group consisting of a polyester-based resin, a polyimide-based resin, a cyclic olefin polymer resin, polyethersulfone, polycarbonate, or a polyolefin-based resin.

The first substrate (100) may include a polyester resin as a main component. The first substrate (100) may include polyethylene terephthalate. The first substrate (100) may include the polyethylene terephthalate in an amount of about 90 wt% or more based on the total composition. The first substrate (100) may include the polyethylene terephthalate in an amount of about 95 wt% or more based on the total composition. The first substrate (100) may include the polyethylene terephthalate in an amount of about 97 wt% or more based on the total composition. The first substrate (100) may include the polyethylene terephthalate in an amount of about 98 wt% or more based on the total composition.

The first substrate (100) may include a uniaxially or biaxially stretched polyethylene terephthalate film. The first substrate (100) may include a polyethylene terephthalate film stretched about 2 to about 5 times in the longitudinal direction and/or the width direction.

The above first substrate (100) can have high mechanical properties to reinforce the glass when applied to a window of a building or vehicle.

The first substrate (100) may have a tensile strength of about 7 kgf/mm2 to about 40 kgf/mm2 in the longitudinal direction. The first substrate (100) may have a tensile strength of about 8 kgf/mm2 to about 35 kgf/mm2 in the longitudinal direction.

The first substrate (100) may have a tensile strength of about 7 kgf/mm2 to about 40 kgf/mm2 in the width direction. The first substrate (100) may have a tensile strength of about 8 kgf/mm2 to about 35 kgf/mm2 in the width direction.

The first substrate (100) may have a modulus of about 200 kgf/mm2 to about 400 kgf/mm2 in the longitudinal direction. The first substrate (100) may have a modulus of about 250 kgf/mm2 to about 350 kgf/mm2 in the longitudinal direction. The first substrate (100) may have a modulus of about 250 kgf/mm2 to about 270 kgf/mm2 in the longitudinal direction.

The first substrate (100) may have a modulus of about 200 kgf/mm2 to about 400 kgf/mm2 in the width direction. The first substrate (100) may have a modulus of about 250 kgf/mm2 to about 350 kgf/mm2 in the width direction. The first substrate (100) may have a modulus of about 250 kgf/mm2 to about 270 kgf/mm2 in the width direction.

The first substrate (100) may have a fracture elongation of about 30% to about 150% in the longitudinal direction. The first substrate (100) may have a fracture elongation of about 30% to about 130% in the longitudinal direction. The first substrate (100) may have a fracture elongation of about 40% to about 120% in the longitudinal direction.

The first substrate (100) may have a fracture elongation of about 30% to about 150% in the longitudinal direction. The first substrate (100) may have a fracture elongation of about 30% to about 130% in the longitudinal direction. The first substrate (100) may have a fracture elongation of about 40% to about 120% in the longitudinal direction.

The first substrate (100) may have a fracture elongation of about 30% to about 150% in the width direction. The first substrate (100) may have a fracture elongation of about 30% to about 130% in the width direction. The first substrate (100) may have a fracture elongation of about 40% to about 120% in the width direction.

The above modulus, the above breaking elongation and the above tensile strength can be measured according to KS B 5521.

Additionally, the modulus, the tensile strength and the elongation at break can be measured by ASTM D882.

Since the first substrate (100) has the improved mechanical strength as described above, it can efficiently protect the first transparent electrode (300), the second transparent electrode (400), the first discoloration layer (500), the second discoloration layer (600), and the electrolyte layer (700). In addition, since the first substrate (100) has the improved mechanical strength as described above, it can efficiently reinforce the mechanical strength of the glass to which it is to be attached.

In addition, the first substrate (100) may have high chemical resistance. Accordingly, even if the electrolyte included in the electrolyte leaks onto the first substrate (100), damage to the surface of the first substrate (100) may be minimized.

The first substrate (100) may have improved optical properties. The total light transmittance of the first substrate (100) may be about 55% or more. The total light transmittance of the first substrate (100) may be about 70% or more. The total light transmittance of the first substrate (100) may be about 75% to about 99%. The total light transmittance of the first substrate (100) may be about 80% to about 99%.

The haze of the first substrate (100) may be less than about 20%. It may be from about 0.1% to about 20%. The haze of the first substrate (100) may be from about 0.1% to about 10%. The haze of the first substrate (100) may be from about 0.1% to about 7%.

The above light transmittance and haze can be measured by ASTM D 1003, etc.

Since the first substrate (100) has appropriate light transmittance and haze, the electrochromic element according to the embodiment can have improved optical characteristics. That is, since the first substrate (100) has appropriate light transmittance and haze, the electrochromic element according to the embodiment can be applied to a window to appropriately control the transmittance, minimize distortion of an image from the outside, and have an improved appearance.

In addition, the first substrate (100) may have an in-plane phase difference of about 100 nm to about 4000 nm. The first substrate (100) may have an in-plane phase difference of about 200 nm to about 3500 nm. The first substrate (100) may have an in-plane phase difference of about 200 nm to about 3000 nm.

The first substrate (100) may have an in-plane phase difference of about 7000 nm or more. The first substrate (100) may have an in-plane phase difference of about 7000 nm to about 50000 nm. The first substrate (100) may have an in-plane phase difference of about 8000 nm to about 20000 nm.

The above in-plane phase difference can be derived from the refractive index and thickness according to the direction of the first substrate (100).

Since the first substrate (100) above has an in-plane phase difference as described above, the electrochromic film according to the embodiment can have an improved appearance.

The thickness of the first substrate (100) may be about 10 ㎛ to about 200 ㎛. The thickness of the first substrate (100) may be about 23 ㎛ to about 150 ㎛. The thickness of the first substrate (100) may be about 30 ㎛ to about 120 ㎛.

The above first substrate (100) may include an organic or inorganic filler. The organic or inorganic filler may perform an anti-blocking agent function.

The average particle diameter of the above filler may be from about 0.1 ㎛ to about 5 ㎛. The average particle diameter of the above filler may be from about 0.1 ㎛ to about 3 ㎛. The average particle diameter of the above filler may be from about 0.1 ㎛ to about 1 ㎛.

The above filler may be selected from the group consisting of silica particles, barium sulfate particles, alumina particles or titania particles.

In addition, the filler may be included in the first substrate (100) in an amount of about 0.01 wt% to about 3 wt% based on the entire first substrate (100). The filler may be included in the first substrate (100) in an amount of about 0.05 wt% to about 2 wt% based on the entire first substrate (100).

The first substrate (100) may have a single-layer structure. For example, the first substrate (100) may be a single-layer polyester film.

The first substrate (100) may have a multilayer structure. For example, the first substrate (100) may be a multilayer coextruded film. The multilayer coextruded structure may include a center layer, a first surface layer, and a second surface layer. The filler may be included in the first surface layer and the second surface layer.

The second substrate (200) faces the first substrate (100). The second substrate (200) is placed on the first substrate (100). One end of the second substrate (200) may be placed so as to be misaligned with one end of the first substrate (100). The other end of the second substrate (200) may be placed so as to be misaligned with the other end of the first substrate (100).

The second substrate (200) supports, together with the first substrate (100), the first transparent electrode (300), the first discoloration layer (500), the second discoloration layer (600), the second transparent electrode (400), and the electrolyte layer (700).

In addition, the second substrate (200) sandwiches the first transparent electrode (300), the first discoloration layer (500), the second discoloration layer (600), the second transparent electrode (400), and the electrolyte layer (700) together with the first substrate (100). The second substrate (200) can protect the first transparent electrode (300), the first discoloration layer (500), the second discoloration layer (600), the second transparent electrode (400), and the electrolyte layer (700) together with the first substrate (100) from external physical impact and chemical impact.

The second substrate (200) may include a polymer resin. The second substrate (200) may include at least one selected from the group consisting of a polyester-based resin, a polyimide-based resin, a cyclic olefin polymer resin, polyethersulfone, polycarbonate, or a polyolefin-based resin.

The second substrate (200) may include a polyester resin as a main component. The second substrate (200) may include polyethylene terephthalate. The second substrate (200) may include the polyethylene terephthalate in an amount of about 90 wt% or more based on the total composition. The second substrate (200) may include the polyethylene terephthalate in an amount of about 95 wt% or more based on the total composition. The second substrate (200) may include the polyethylene terephthalate in an amount of about 97 wt% or more based on the total composition. The second substrate (200) may include the polyethylene terephthalate in an amount of about 98 wt% or more based on the total composition.

The second substrate (200) may include a uniaxially or biaxially stretched polyethylene terephthalate film. The second substrate (200) may include a polyethylene terephthalate film stretched about 2 to about 5 times in the longitudinal direction and/or the width direction.

The above second substrate (200) may have high mechanical properties to reinforce glass included in the window when applied to a window of a building or vehicle.

The second substrate (200) may have a tensile strength of about 7 kgf/mm2 to about 40 kgf/mm2 in the longitudinal direction. The second substrate (200) may have a tensile strength of about 8 kgf/mm2 to about 35 kgf/mm2 in the longitudinal direction.

The second substrate (200) may have a tensile strength of about 7 kgf/mm2 to about 40 kgf/mm2 in the width direction. The second substrate (200) may have a tensile strength of about 8 kgf/mm2 to about 35 kgf/mm2 in the width direction.

The second substrate (200) may have a modulus of about 200 kgf/mm2 to about 400 kgf/mm2 in the longitudinal direction. The second substrate (200) may have a modulus of about 250 kgf/mm2 to about 350 kgf/mm2 in the longitudinal direction. The second substrate (200) may have a modulus of about 250 kgf/mm2 to about 270 kgf/mm2 in the longitudinal direction.

The second substrate (200) may have a modulus of about 200 kgf/mm2 to about 400 kgf/mm2 in the width direction. The second substrate (200) may have a modulus of about 250 kgf/mm2 to about 350 kgf/mm2 in the width direction. The second substrate (200) may have a modulus of about 250 kgf/mm2 to about 270 kgf/mm2 in the width direction.

The second substrate (200) may have a fracture elongation of about 30% to about 150% in the longitudinal direction. The second substrate (200) may have a fracture elongation of about 30% to about 130% in the longitudinal direction. The second substrate (200) may have a fracture elongation of about 40% to about 120% in the longitudinal direction.

The second substrate (200) may have a fracture elongation of about 30% to about 150% in the longitudinal direction. The second substrate (200) may have a fracture elongation of about 30% to about 130% in the longitudinal direction. The second substrate (200) may have a fracture elongation of about 40% to about 120% in the longitudinal direction.

The second substrate (200) may have a fracture elongation of about 30% to about 150% in the width direction. The second substrate (200) may have a fracture elongation of about 30% to about 130% in the width direction. The second substrate (200) may have a fracture elongation of about 40% to about 120% in the width direction.

Since the second substrate (200) has the improved mechanical strength as described above, it can efficiently protect the first transparent electrode (300), the second transparent electrode (400), the first discoloration layer (500), the second discoloration layer (600), and the electrolyte layer (700). In addition, since the second substrate (200) has the improved mechanical strength as described above, it can efficiently reinforce the mechanical strength of the glass to which it is to be attached.

In addition, the second substrate (200) may have high chemical resistance. Accordingly, even if the electrolyte included in the electrolyte leaks onto the second substrate (200), damage to the surface of the second substrate (200) may be minimized.

The second substrate (200) may have improved optical properties. The total light transmittance of the second substrate (200) may be about 55% or more. The total light transmittance of the second substrate (200) may be about 70% or more. The total light transmittance of the second substrate (200) may be about 75% to about 99%. The total light transmittance of the second substrate (200) may be about 80% to about 99%.

The haze of the second substrate (200) may be less than about 20%. It may be from about 0.1% to about 20%. The haze of the second substrate (200) may be from about 0.1% to about 10%. The haze of the second substrate (200) may be from about 0.1% to about 7%.

Since the second substrate (200) has appropriate light transmittance and haze, the electrochromic element according to the embodiment can have improved optical characteristics. That is, since the second substrate (200) has appropriate light transmittance and haze, the electrochromic element according to the embodiment can be applied to a window to appropriately control the transmittance, minimize distortion of an image from the outside, and have an improved appearance.

In addition, the second substrate (200) may have an in-plane phase difference of about 100 nm to about 4000 nm. The second substrate (200) may have an in-plane phase difference of about 200 nm to about 3500 nm. The second substrate (200) may have an in-plane phase difference of about 200 nm to about 3000 nm.

The second substrate (200) may have an in-plane phase difference of about 7000 nm or more. The second substrate (200) may have an in-plane phase difference of about 7000 nm to about 50000 nm. The second substrate (200) may have an in-plane phase difference of about 8000 nm to about 20000 nm.

The above in-plane phase difference can be derived from the refractive index and thickness according to the direction of the second substrate (200).

Since the second substrate (200) has an in-plane phase difference as described above, the electrochromic element according to the embodiment can have an improved appearance.

The thickness of the second substrate (200) may be about 10 ㎛ to about 200 ㎛. The thickness of the first substrate (100) may be about 23 ㎛ to about 150 ㎛. The thickness of the first substrate (100) may be about 30 ㎛ to about 120 ㎛.

The second substrate (200) may include an organic or inorganic filler. The organic or inorganic filler may perform an anti-blocking agent function.

The average particle diameter of the above filler may be from about 0.1 ㎛ to about 5 ㎛. The average particle diameter of the above filler may be from about 0.1 ㎛ to about 3 ㎛. The average particle diameter of the above filler may be from about 0.1 ㎛ to about 1 ㎛.

The above filler may be selected from the group consisting of silica particles, barium sulfate particles, alumina particles or titania particles.

In addition, the filler may be included in the second substrate (200) in a content of about 0.01 wt% to about 3 wt% based on the entire second substrate (200). The filler may be included in the second substrate (200) in a content of about 0.05 wt% to about 2 wt% based on the entire second substrate (200).

The second substrate (200) may have a single-layer structure. For example, the second substrate (200) may be a single-layer polyester film.

The second substrate (200) may have a multilayer structure. For example, the second substrate (200) may be a multilayer coextruded film.

The first substrate (100) and the second substrate (200) may be flexible. Accordingly, the electrochromic element according to the embodiment may be flexible overall.

The above ultraviolet ray blocking layer (800) is disposed on the first substrate (100). The above ultraviolet ray blocking layer (800) is disposed under the first transparent electrode (300). The above ultraviolet ray blocking layer (800) is disposed between the first substrate (100) and the first transparent electrode (300).

The above ultraviolet ray blocking layer (800) may include an ultraviolet ray absorbent.

The above ultraviolet absorbent may be at least one selected from the group consisting of benzoxazinone-based, triazine-based, benzotriazole-based, and benzophenone-based ultraviolet absorbents.

Examples of commercially available UV absorbers include benzoxazinones such as CYASORB UV-3853S from Cytec; triazines such as CYASORB UV-1164 from Cytec, and TINUVIN 1577, TINUVIN P, TINUVIN 234, TINUVIN 326, TINUVIN 328, TINUVIN 329, TINUVIN 571, TINUVIN 400, TINUVIN 479 from BASF; Benzotriazole products include CYASORB UV-2337, CYASORB UV-5411 from Ciba, TINUVIN 360, TINUVIN 213, TINUVIN 99-2, TINUVIN 171, TINUVIN 328, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130 from BASF, and SONGSORB 1000, SONGSORB 2340, SONGSORB 3200, SONGSORB 3260, SONGSORB 3270, SONGSORB 3280 from Songwon Industrial; Benzophenone series products include CYASORB UV-9, CYASORB UV-24, CYASORB UV-531 from Cytec, CHIMASSORB 81 from Ciba, and SONGSORB 8100 from Songwon Industrial. Each UV absorber can be used alone or in combination of two or more types.

The above ultraviolet absorbent may have a first absorption maximum in a wavelength range of about 290 nm to about 310 nm, and a second absorption maximum in a wavelength range of about 330 nm to about 350 nm.

The above ultraviolet absorbent may have a first absorption maximum in a wavelength range of about 280 nm to about 300 nm, and a second absorption maximum in a wavelength range of about 320 nm to about 340 nm.

The above ultraviolet absorbent may have a first absorption maximum in a wavelength range of about 270 nm to about 290 nm, and a second absorption maximum in a wavelength range of about 330 nm to about 350 nm.

The above ultraviolet absorbent may have an absorption maximum in a wavelength range of about 290 nm to about 310 nm. The above ultraviolet absorbent may have an absorption maximum in a wavelength range of about 300 nm to about 320 nm.

Since the above ultraviolet absorbent has the absorption maximum as described above, it can effectively block ultraviolet rays incident on the first discoloration layer (500). Accordingly, the ultraviolet absorbent can effectively prevent electrons generated by ultraviolet rays incident on the first discoloration layer (500).

The above UV-blocking layer (800) may further include a photocurable resin. The photocurable resin may include a photocurable (meth)acrylate oligomer and/or a photocurable (meth)acrylate monomer.

The above photocurable (meth)acrylate oligomer may be at least one selected from the group consisting of urethane (meth)acrylate, polyester (meth)acrylate, and epoxy (meth)acrylate. Examples of commercially available oligomers include EB-1290 (SK Cytec), Adeka Optomer KR·BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka Co., Ltd.); Goei Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (Goei Kagaku Co., Ltd.); Seika Beam PHC2210(S), PHC X-9(K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (Dainichi Seika High School Co., Ltd.); KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL 29201, UVECRYL 29202 (Daicel UCB Co., Ltd.); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (Dainippon Ink & Kagaku Kogyo Co., Ltd.); OreX No.340 Clear (Chugoku Paint Co., Ltd.); Sanrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (Sanyo Kasei Kogyo Co., Ltd.); Examples include SP-1509, SP-1507 (Showa Kofunshi Co., Ltd.); RCC-15C (Grace Japan Co., Ltd.); Aronix M-6100, M-8030, M-8060 (Toa Kosei Co., Ltd.).

The above photocurable (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri/penta(meth)acrylate, dipentaerythritol penta/hexa(meth)acrylate, isoborneol (meth)acrylate, phenoxyethyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, ethylhexyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentane (meth)acrylate, tetrahydrofuranol (meth)acrylate, lauryl (meth)acrylate, styryl (meth)acrylate, Isodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyisopropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, etc. can be used, but are not limited to these.

The above photocurable resin can be used by mixing one or more of the photocurable (meth)acrylate oligomers and photocurable (meth)acrylate monomers exemplified above, and the type and content thereof are not particularly limited.

The above UV-blocking layer (800) includes a photo-curing initiator. The photo-curing initiator may include a phosphine oxide series photo-initiator having an absorption wavelength of 400 nm or more. The above photoinitiator may be at least one selected from the group consisting of bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Igacure-819).

The photocurable resin may be included in the UV blocking layer (800) in an amount of about 60 wt%% to about 98 wt% based on 100 wt% of the entire UV blocking layer (800). The photocurable resin may be included in the UV blocking layer (800) in an amount of about 70 wt%% to about 90 wt% based on 100 wt% of the entire UV blocking layer (800). The photocurable resin may be included in the UV blocking layer (800) in an amount of about 80 wt%% to about 90 wt% based on 100 wt% of the entire UV blocking layer (800).

The above ultraviolet absorber may be included in the ultraviolet blocking layer (800) in an amount of about 1 part by weight to about 20 parts by weight based on 100 parts by weight of the photocurable resin. The above ultraviolet absorber may be included in the ultraviolet blocking layer (800) in an amount of about 1 part by weight to about 15 parts by weight based on 100 parts by weight of the photocurable resin. The above ultraviolet absorber may be included in the ultraviolet blocking layer (800) in an amount of about 1 part by weight to about 10 parts by weight based on 100 parts by weight of the photocurable resin. The above ultraviolet absorber may be included in the ultraviolet blocking layer (800) in an amount of about 3 parts by weight to about 10 parts by weight based on 100 parts by weight of the photocurable resin.

The photocuring initiator may be included in the UV blocking layer (800) in an amount of about 1 part by weight to about 20 parts by weight based on 100 parts by weight of the photocurable resin. The photocuring initiator may be included in the UV blocking layer (800) in an amount of about 3 parts by weight to about 20 parts by weight based on 100 parts by weight of the photocurable resin. The photocuring initiator may be included in the UV blocking layer (800) in an amount of about 5 parts by weight to about 15 parts by weight based on 100 parts by weight of the photocurable resin. The photocuring initiator may be included in the UV blocking layer (800) in an amount of about 10 parts by weight to about 20 parts by weight based on 100 parts by weight of the photocurable resin.

Since the above ultraviolet ray blocking layer (800) contains the photocurable resin, the ultraviolet ray absorber, and the photocuring initiator in the above ranges, it can have appropriate mechanical properties and appropriate ultraviolet ray blocking properties.

Accordingly, the first discoloration layer (500) can suppress electrons generated by ultraviolet rays incident from the outside.

The above UV blocking layer (800) may further include a UV stabilizer, a heat stabilizer, an antioxidant, or a surfactant.

The thickness of the above UV blocking layer (800) may be about 0.1 ㎛ to about 20 ㎛. The thickness of the above UV blocking layer (800) may be about 1 ㎛ to about 20 ㎛. The thickness of the above UV blocking layer (800) may be about 1 ㎛ to about 10 ㎛. The thickness of the above UV blocking layer (800) may be about 3 ㎛ to about 8 ㎛.

Since the above ultraviolet ray blocking layer (800) has a thickness within the above range, it can have appropriate mechanical properties and appropriate ultraviolet ray blocking properties.

The ultraviolet ray blocking laminate including the first substrate (100) and the ultraviolet ray blocking layer (800) can have low ultraviolet ray transmittance.

The above ultraviolet ray blocking laminate can have a transmittance of less than about 20% for light in a wavelength range of about 250 nm to about 400 nm. The above ultraviolet ray blocking laminate can have a transmittance of less than about 15% for light in a wavelength range of about 250 nm to about 400 nm. The above ultraviolet ray blocking laminate can have a transmittance of less than about 10% for light in a wavelength range of about 250 nm to about 400 nm.

The above ultraviolet ray blocking laminate can have a transmittance of less than about 20% for light having a wavelength of about 350 nm. The above ultraviolet ray blocking laminate can have a transmittance of less than about 15% for light having a wavelength of about 350 nm. The above ultraviolet ray blocking laminate can have a transmittance of less than about 10% for light having a wavelength of about 350 nm.

The above ultraviolet ray blocking laminate can have a transmittance of greater than about 60% for light in a wavelength range of about 400 nm to about 650 nm. The above ultraviolet ray blocking laminate can have a transmittance of greater than about 70% for light in a wavelength range of about 400 nm to about 650 nm. The above ultraviolet ray blocking laminate can have a transmittance of greater than about 80% for light in a wavelength range of about 400 nm to about 650 nm.

The above ultraviolet ray blocking laminate can have a transmittance of greater than about 60% for light having a wavelength of about 550 nm. The above ultraviolet ray blocking laminate can have a transmittance of greater than about 70% for light having a wavelength of about 550 nm. The above ultraviolet ray blocking laminate can have a transmittance of greater than about 80% for light having a wavelength of about 550 nm.

Since the above ultraviolet ray blocking laminate has the ultraviolet ray transmittance and visible light transmittance as described above, it can have an improved appearance while suppressing electrons caused by external light.

FIG. 2 is a cross-sectional view illustrating one section of an electrochromic element according to another embodiment.

Referring to FIG. 2, the ultraviolet ray blocking layer (800) may be placed under the first substrate (100). The ultraviolet ray blocking layer (800) may be directly placed on the lower surface of the first substrate (100). The ultraviolet ray blocking layer (800) may be directly coated on the lower surface of the first substrate (100) and formed by curing.

In contrast, the ultraviolet ray blocking layer (800) and the first substrate (100) may be formed as a single layer. The ultraviolet ray absorbent may be included in the first substrate (100). Accordingly, the first substrate (100) may perform both a support layer function and an ultraviolet ray blocking function.

The first transparent electrode (300) is disposed on the first substrate (100). The first transparent electrode (300) is disposed on the ultraviolet ray blocking layer (800). The first transparent electrode (300) can be formed by being deposited on the ultraviolet ray blocking layer (800).

The first transparent electrode (300) may include at least one selected from the group consisting of tin oxide, zinc oxide, silver (Ag), chromium (Cr), indium tin oxide (ITO), fluorine doped tin oxide (FTO), aluminum doped zinc oxide (AZO), gallium doped zinc oxide (GZO), antimony doped tin oxide (ATO), indium zinc oxide (IZO), niobium doped titanium oxide (NTO), or cadmium tin oxide (CTO).

Additionally, the first transparent electrode (300) may include graphene, silver nanowires, and/or metal mesh.

The first transparent electrode (300) may have a light transmittance of about 80% or more. The first transparent electrode (300) may have a light transmittance of about 85% or more. The first transparent electrode (300) may have a light transmittance of about 88% or more.

The first transparent electrode (300) may have a haze of less than about 10%. The first transparent electrode (300) may have a haze of less than about 7%. The first transparent electrode (300) may have a haze of less than about 5%.

The sheet resistance of the first transparent electrode (300) may be about 1Ω/sq to 60Ω/sq. The sheet resistance of the first transparent electrode (300) may be about 1Ω/sq to 40Ω/sq. The sheet resistance of the first transparent electrode (300) may be about 1Ω/sq to 30Ω/sq.

The thickness of the first transparent electrode (300) may be about 50 nm to about 50 μm. The thickness of the first transparent electrode (300) may be about 100 nm to about 10 μm. The thickness of the first transparent electrode (300) may be about 150 nm to about 5 μm.

The first transparent electrode (300) is electrically connected to the first discoloration layer (500). In addition, the first transparent electrode (300) is electrically connected to the electrolyte layer (700) through the first discoloration layer (500).

The second transparent electrode (400) is positioned below the second substrate (200). The second transparent electrode (400) may be formed by being deposited on the second substrate (200). In addition, a hard coating layer may be further included between the second transparent electrode (400) and the second substrate (200).

The second transparent electrode (400) may include at least one selected from the group consisting of tin oxide, zinc oxide, silver (Ag), chromium (Cr), indium tin oxide (ITO), fluorine doped tin oxide (FTO), aluminum doped zinc oxide (AZO), gallium doped zinc oxide (GZO), antimony doped tin oxide (ATO), indium zinc oxide (IZO), niobium doped titanium oxide (NTO), or cadmium tin oxide (CTO).

Additionally, the second transparent electrode (400) may include graphene, silver nanowires, and/or metal mesh.

The second transparent electrode (400) may have a total light transmittance of about 80% or more. The second transparent electrode (400) may have a total light transmittance of about 85% or more. The second transparent electrode (400) may have a total light transmittance of about 88% or more.

The second transparent electrode (400) may have a haze of less than about 10%. The second transparent electrode (400) may have a haze of less than about 7%. The second transparent electrode (400) may have a haze of less than about 5%.

The surface resistance of the second transparent electrode (400) may be about 1Ω/sq to 60Ω/sq. The surface resistance of the second transparent electrode (400) may be about 1Ω/sq to 40Ω/sq. The surface resistance of the second transparent electrode (400) may be about 1Ω/sq to 30Ω/sq.

The thickness of the second transparent electrode (400) may be about 50 nm to about 50 μm. The thickness of the second transparent electrode (400) may be about 100 nm to about 10 μm. The thickness of the second transparent electrode (400) may be about 150 nm to about 5 μm.

The second transparent electrode (400) is electrically connected to the second discoloration layer (600). In addition, the second transparent electrode (400) is electrically connected to the electrolyte layer (700) through the second discoloration layer (600).

The first discoloration layer (500) is disposed on the first transparent electrode (300). The first discoloration layer (500) can be directly disposed on the upper surface of the first transparent electrode (300). The first discoloration layer (500) can be directly electrically connected to the first transparent electrode (300).

The first discoloration layer (500) is electrically connected to the first transparent electrode (300). The first discoloration layer (500) can be directly connected to the first transparent electrode (300). In addition, the first discoloration layer (500) is electrically connected to the electrolyte layer (700). The first discoloration layer (500) can be electrically connected to the electrolyte layer (700).

The first discoloring layer (500) can change color when supplied with electrons. The first discoloring layer (500) can include a first electrochromic material that changes color when supplied with electrons. The first electrochromic material can include at least one selected from the group consisting of tungsten oxide, niobium pentoxide, vanadium pentoxide, titanium oxide, molybdenum oxide, vilogen, and poly(3,4-ethylenedioxythiophene; PEDOT).

The first discoloration layer (500) may include the first electrochromic material in the form of particles. The tungsten oxide, niobium pentoxide, vanadium pentoxide, titanium oxide, and molybdenum oxide may be particles having an average particle diameter of about 1 nm to about 200 nm. The average particle diameter of the first electrochromic material may be about 5 nm to about 100 nm. The average particle diameter of the first electrochromic material may be about 10 nm to about 50 nm.

The first discoloration layer (500) may include the first electrochromic material in an amount of about 70 wt% to about 98 wt% based on the total weight of the first discoloration layer (500). The first discoloration layer (500) may include the first electrochromic material in an amount of about 80 wt% to about 96 wt% based on the total weight of the first discoloration layer (500). The first discoloration layer (500) may include the first electrochromic material in an amount of about 85 wt% to about 94 wt% based on the total weight of the first discoloration layer (500).

Since the first chromic layer (500) includes the first electrochromic material in the average particle diameter and weight range, the electrochromic element according to the embodiment can have improved optical characteristics and electrochromic characteristics.

In addition, the first discoloration layer (500) may further include a binder. The binder may be an inorganic binder. The binder may include silica gel. The binder may be formed by a silica sol including tetramethoxysilane or methyltrimethoxysilane.

The first discoloration layer (500) may contain the binder in an amount of about 1 wt% to 20 wt% based on the total weight of the first discoloration layer (500). The first discoloration layer (500) may contain the binder in an amount of about 5 wt% to 15 wt% based on the total weight of the first discoloration layer (500). The first discoloration layer (500) may contain the binder in an amount of about 7 wt% to 13 wt% based on the total weight of the first discoloration layer (500).

The second discoloration layer (600) is disposed under the second transparent electrode (400). The second discoloration layer (600) can be disposed directly on the lower surface of the second transparent electrode (400). The second discoloration layer (600) can be electrically directly connected to the second transparent electrode (400).

The second discoloration layer (600) is electrically connected to the second transparent electrode (400). The second discoloration layer (600) can be directly connected to the second transparent electrode (400). In addition, the second discoloration layer (600) is electrically connected to the electrolyte layer (700). The second discoloration layer (600) can be electrically connected to the electrolyte layer (700).

The second discoloration layer (600) can change color by losing electrons. The second discoloration layer (600) can include a second electrochromic material that changes color by being oxidized by losing electrons. The second discoloration layer (600) can include at least one selected from the group consisting of Prussian blue, nickel oxide, and iridium oxide.

The second discoloration layer (600) may include the second electrochromic material in the form of particles. The Prussian blue, nickel oxide, and iridium oxide may be particles having a particle size of about 1 nm to about 200 nm.

Additionally, the second discoloration layer (600) may further include the binder.

The second substrate (200), the second transparent electrode (400), and the second discoloration layer (600) are included in the second laminate. That is, the second laminate includes the second substrate (200), the second transparent electrode (400), and the second discoloration layer (600). The second laminate may be composed of the second substrate (200), the second transparent electrode (400), and the second discoloration layer (600).

The electrolyte layer (700) is disposed on the first discoloration layer (500). In addition, the electrolyte layer (700) is disposed below the second discoloration layer (600). The electrolyte layer (700) is disposed between the first discoloration layer (500) and the second discoloration layer (600).

The above electrolyte layer (700) may include a solid polymer electrolyte containing metal ions or an inorganic hydrate, etc. The above electrolyte layer (700) may include lithium ions (Li+), sodium ions (Na+), potassium ions (K+), etc.

Specifically, Poly-AMPS, PEO/LiCF ₃ SO ₃ , etc. can be used as the solid polymer electrolyte, and Sb ₂ O ₅ ㆍ 4H ₂ O, etc. can be used as the inorganic hydrate.

In addition, the electrolyte layer (700) is configured to provide electrolyte ions involved in the electrochromic reaction. The electrolyte ions may be monovalent cations such as, for example, H+, Li+, Na+, K+, Rb+, or Cs+.

The above electrolyte layer (700) may include an electrolyte. Examples of the electrolyte include, without limitation, a liquid electrolyte, a gel polymer electrolyte, or an inorganic solid electrolyte. In addition, the electrolyte may be used in the form of a single layer or film so as to be laminated together with the electrode or substrate.

The type of electrolyte salt used in the electrolyte layer (700) is not particularly limited, as long as it can include a compound capable of providing a monovalent cation, i.e., H+, Li+, Na+, K+, Rb+ or Cs+. For example, the electrolyte layer (700) may include a lithium salt compound, such as LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCl, LiBr, LiI, LiB ₁₀ Cl ₁₀ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiAsF ₆ , LiSbF ₆ , LiAlCl ₄ , CH ₃ SO ₃ Li, CF ₃ SO ₃ Li or (CF ₃ SO ₂ ) ₂ NLi; or a sodium salt compound, such as NaClO ₄ .

In one example, the electrolyte layer (700) may include a compound containing Cl or F element as an electrolyte salt. Specifically, the electrolyte layer (700) may include one or more electrolyte salts selected from LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCl, LiB ₁₀ Cl ₁₀ , _{LiCF 3 SO 3 , LiCF 3} CO ₂ , LiAsF ₆ , LiSbF _{6 , LiAlCl 4} , CF ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, and NaClO ₄ .

The above electrolyte may additionally include a carbonate compound as a solvent. Since the carbonate compound has a high dielectric constant, it can increase ionic conductivity. As a non-limiting example, a solvent such as PC (propylene carbonate), EC (ethylene carbonate), DMC (dimethyl carbonate), DEC (diethyl carbonate), or EMC (ethylmethyl carbonate) can be used as the carbonate compound.

In another example, when the electrolyte layer (700) includes a gel polymer electrolyte, the electrolyte layer (700) may include poly-vinyl sulfonic acid, poly-styrene sulfonic acid, polyethylene sulfonic acid, poly-2-acrylamido-2methyl-propane sulfonic acid, poly-perfluoro sulfonic acid, poly-toluene sulfonic acid, poly-vinyl alcohol, poly-ethylene imine, poly-vinyl pyrrolidone, poly-ethylene oxide (PEO), poly-propylene oxide (PPO), It may include polymers such as poly-(ethylene oxide, siloxane) (PEOS), poly-(ethylene glycol, siloxane), poly-(propylene oxide, siloxane), poly-(ethylene oxide, methyl methacrylate) (PEO-PMMA), poly-(ethylene oxide, acrylic acid) (PEO PAA), poly-(propylene glycol, methyl methacrylate) (PPG PMMA), poly-ethylene succinate or poly-ethylene adipate. In one example, a mixture of two or more of the above-listed polymers or a copolymer of two or more of the above-listed polymers may be used as the polymer electrolyte.

In addition, the electrolyte layer (700) may include a curable resin that can be cured by ultraviolet irradiation or heat. The curable resin may be selected from at least one selected from the group consisting of an acrylate-based oligomer, a polyethylene glycol-based oligomer, a urethane-based oligomer, a polyester-based oligomer, polyethylene glycol dimethyl, or polyethylene glycol diacrylate. In addition, the electrolyte layer (700) may include a photocuring initiator and/or a thermal curing initiator.

The thickness of the electrolyte layer (700) may be about 10 ㎛ to about 200 ㎛. The thickness of the electrolyte layer (700) may be about 50 ㎛ to about 150 ㎛.

The electrolyte layer (700) may have a transmittance within a range of 60% to 95%. Specifically, the electrolyte layer (700) may have a transmittance within a range of 60% to 95% for visible light having a wavelength of 380 nm to 780 nm, more specifically, a wavelength of 400 nm or a wavelength of 550 nm. The transmittance may be measured using a known haze meter (HM).

The electrochromic element according to the embodiment may further include a sealing member (not shown).

The sealing member comprises a curable resin. The sealing member may comprise a thermosetting resin and/or a photocurable resin.

Examples of the thermosetting resin include epoxy resin, melamine resin, urea resin, or unsaturated polyester resin. In addition, examples of the epoxy resin include phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, biphenyl novolac-type epoxy resin, trisphenol novolac-type epoxy resin, dicyclopentadiene novolac-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, 2,2'-diarylbisphenol A-type epoxy resin, bisphenol S-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, propylene oxide-added bisphenol A-type epoxy resin, biphenyl-type epoxy resin, naphthalene-type epoxy resin, resorcinol-type epoxy resin, or glycidyl amines.

Additionally, the sealing member may further include a heat curing agent. 1, 3-bis[hydrazinocarbonoethyl 5-isopropyl hydantoin], hydrazide compounds such as adipic acid dihydrazide; dicyandiamide, guanidine derivatives, 1-cyanoethyl-2-phenyl imidazole, N-[2-(2-methyl-1-imidazolyl) ethyl]urea, 2, 4-diamino-6-[2'-methylimidazolyl(1')]-ethyl-s-thoriazine, N,N'-bis(2-methyl-1-imidazolyl ethyl)urea, N,N'-(2-methyl-1-imidazolyl ethyl)-azipoamido, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 2-imidazoline-2-thiol, 2, Examples include 2'-thio diethanethiol, addition products of various amines and epoxy resins, etc.

The first sealing portion may include a photocurable resin. Examples of the photocurable resin include an acrylate-based resin such as urethane acrylate. In addition, the sealing portion may further include a photocuring initiator. The photocuring initiator may be at least one selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.

In addition, the sealing member may further include a moisture absorbent such as zeolite and/or silica. In addition, the sealing member may further include an inorganic filler. The inorganic filler may be a material having high insulating properties, transparency, and durability. Examples of the inorganic filler include silicon, aluminum, zirconia, or mixtures thereof.

Additionally, the electrochromic element according to the embodiment may further include a first bus bar (not shown) and a second bus bar (not shown).

The first bus bar may be placed on the first transparent electrode (300). The first bus bar may be connected to the first transparent electrode (300).

The first bus bar may be electrically connected to the first transparent electrode (300). The first bus bar may be in direct contact with the upper surface of the first transparent electrode (300). The first bus bar may be connected to the first transparent electrode (300) via solder.

The second bus bar is positioned below the second transparent electrode (400). The second bus bar is connected to the second transparent electrode (400).

The second bus bar may be electrically connected to the second transparent electrode (400). The second bus bar may be in direct contact with the lower surface of the second transparent electrode (400). The second bus bar may be connected to the second transparent electrode (400) through solder.

The first bus bar and/or the second bus bar may include a metal. The first bus bar and/or the second bus bar may include a metal ribbon. The first bus bar and/or the second bus bar may include a conductive paste. The first bus bar and/or the second bus bar may include a binder and a conductive filler.

An electrochromic element according to an embodiment can be manufactured by the following method. FIGS. 3 to 6 are cross-sectional views illustrating a process for manufacturing an electrochromic element according to an embodiment.

Referring to FIG. 3, an ultraviolet ray blocking layer (800) is formed on the first substrate (100).

In order to form the above ultraviolet ray blocking layer (800), a photocurable resin composition containing the above ultraviolet ray absorbent is formed.

The photocurable resin composition comprises the photocurable resin, the ultraviolet absorber and the photoinitiator. In addition, the photocurable resin composition may further comprise an organic solvent.

Examples of the above organic solvents include alcohols (methanol, ethanol, isopropanol, butanol, propylene glycol methoxy alcohol, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, etc.), acetates (methyl acetate, ethyl acetate, butyl acetate, propylene glycol methoxy acetate, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, propyl cellosolve, etc.), hydrocarbons (normal hexane, normal heptane, benzene, toluene, xylene, etc.). The above solvents may be used alone or in combination of two or more.

The photocurable resin composition may contain the organic solvent in an amount of about 30 parts by weight to about 200 parts by weight, based on 100 parts by weight of the photocurable resin. The photocurable resin composition may contain the organic solvent in an amount of about 50 parts by weight to about 150 parts by weight, based on 100 parts by weight of the photocurable resin. The photocurable resin composition may contain the organic solvent in an amount of about 70 parts by weight to about 120 parts by weight, based on 100 parts by weight of the photocurable resin.

The above photocurable resin composition can be coated (coating process) on the first substrate (100) by appropriately using a known method such as a die coater, air knife, reverse roll, spray, blade, casting, gravure, micro gravure, or spin coating.

The thickness of the coating layer formed by coating the above curable resin composition may be from about 0.1 ㎛ to about 50 ㎛. The thickness of the coating layer formed by coating the above curable resin composition may be from about 0.5 ㎛ to about 50 ㎛.

After the above curable resin composition is coated, a drying process may be performed. The drying process may be performed at about 40° C. to about 120° C. for about 1 minute to about 5 minutes.

Thereafter, the dried curable resin composition coating layer can be cured by light. As a light source in the curing process, a lamp having a main wavelength of 400 nm or more can be used.

Accordingly, the ultraviolet ray blocking layer (800) is formed on the first substrate (100).

Thereafter, a first transparent electrode (300) is formed on the UV blocking layer (800). The first transparent electrode (300) can be formed by a vacuum deposition process. A metal oxide such as indium tin oxide can be deposited on the first substrate (100) by a sputtering process, etc., to form the first transparent electrode (300).

The first transparent electrode (300) can be formed by a coating process. The first transparent electrode (300) can be formed by coating nano metal wires together with a binder on the first substrate (100). The first transparent electrode (300) can be formed by coating a conductive polymer on the first substrate (100).

In addition, the first transparent electrode (300) can be formed by a patterning process. A metal layer is formed on the first substrate (100) by a sputtering process or the like, and the metal layer is patterned so that a first transparent electrode (300) layer including a metal mesh can be formed on the first substrate (100).

Thereafter, a first discoloration layer (500) is formed on the first transparent electrode (300) layer. The first discoloration layer (500) can be formed by a sol-gel coating process. A first sol solution including a first electrochromic material, a binder, and a solvent can be coated on the first transparent electrode (300) layer. A sol-gel reaction occurs in the coated first sol solution, and the first discoloration layer (500) can be formed.

The first sol solution may contain the first electrochromic material in particle form in an amount of about 5 wt % to about 30 wt % based on the total weight of the solution. The first sol solution may contain the binder in an amount of about 0.5 wt % to about 5 wt % based on the total weight of the solution. The first sol solution may contain the solvent in an amount of about 70 wt % to about 95 wt % based on the total weight of the solution.

The above first sol solution may additionally contain a dispersant.

The solvent may be at least one selected from the group consisting of alcohols, ethers, ketones, esters, and aromatic hydrocarbons. The solvent may be at least one selected from the group consisting of ethanol, propanol, butanol, hexanol, cyclohexanol, diacetone alcohol, ethylene glycol, diethylene glycol, glycerin, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclohexanone, acetoacetate, methyl acetate, ethyl acetate, n-propyl acetate, and i-butyl acetate.

The above binder may be an inorganic binder, as described above.

Referring to FIG. 4, an electrolyte composition for forming an electrolyte layer (700) is formed.

The above electrolyte composition may include a metal salt, an electrolyte, a photocurable resin, and a photocurable initiator. The above photocurable resin may be at least one selected from the group consisting of hexandiol diacrylate (HDDA), tripropyleneglycoldiacrylate (TPGDA), ethyleneglycoldiacrylate (EGDA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxylated triacrylate (TMPEOTA), glycerol propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PETA), or dipentaerythritol hexaacrylate (DPHA).

The above metal salt, the electrolyte and the photocuring initiator may be as described above.

The electrolyte composition is coated on the first discoloration layer (500). Accordingly, an electrolyte composition coating layer (701) is formed on the first discoloration layer (500).

Referring to FIG. 5, a second transparent electrode (400) is formed on a second substrate (200).

The second transparent electrode (400) may be formed by a vacuum deposition process. A metal oxide such as indium tin oxide may be deposited on the second substrate (200) by a sputtering process, etc., to form the second transparent electrode (400).

The second transparent electrode (400) can be formed by a coating process. The second transparent electrode (400) can be formed by coating nano metal wires together with a binder on the second substrate (200). The second transparent electrode (400) can be formed by coating a conductive polymer on the second substrate (200).

In addition, the second transparent electrode (400) can be formed by a patterning process. A metal layer is formed on the second substrate (200) by a sputtering process or the like, and the metal layer is patterned so that a second transparent electrode (400) layer including a metal mesh can be formed on the second substrate (200).

Thereafter, a second chromic layer (600) is formed on the second transparent electrode (400) layer. The second chromic layer (600) can be formed by a sol-gel coating process. A second sol solution including a second electrochromic material, a binder, and a solvent can be coated on the second transparent electrode (400) layer. A sol-gel reaction occurs in the coated second sol solution, and the second chromic layer (600) can be formed.

The second sol solution may contain the second discoloring material in particle form in an amount of about 5 wt% to about 30 wt% based on the total weight of the solution. The second sol solution may contain the binder in an amount of about 0.5 wt% to about 5 wt% based on the total weight of the solution. The second sol solution may contain the solvent in an amount of about 70 wt% to about 95 wt% based on the total weight of the solution.

The above second sol solution may additionally contain a dispersant.

Referring to Fig. 6, the second substrate (200), the second transparent electrode (400), and the second discoloration layer (600) are laminated on the coated electrolyte composition layer (701). At this time, the second discoloration layer (600) is in direct contact with the coated electrolyte composition layer (701).

Thereafter, the coated electrolyte composition layer (701) is cured by light, and a first laminate including the first substrate (100), the first transparent electrode (300), and the first discoloration layer (500) and a second laminate including the second substrate (200), the second transparent electrode (400), and the second discoloration layer (600) are laminated to each other. That is, the first laminate and the second laminate can be adhered to each other by the electrolyte layer (700).

In addition, the electrochromic element according to the embodiment may have light transmittance. Here, the light transmittance may mean light transmittance based on a state in which the electrochromic element is not electrochromic. In addition, the light transmittance may mean total light transmittance.

The light transmittance of the electrochromic element can be from about 50% to about 90%. The light transmittance of the electrochromic element can be from about 55% to about 88%. The light transmittance of the electrochromic element can be from about 68% to about 86%.

The electrochromic element according to the embodiment may have a change in light transmittance. The change in light transmittance is a change in light transmittance after exposure to ultraviolet rays compared to the initial light transmittance.

The above light transmittance change rate can be measured by the following measurement method 1.

[Measurement Method 1]

Through the first substrate (100), ultraviolet rays are irradiated to the electrochromic portion (11) at an intensity of about 7.5 W/㎡ for 1 hour, the first light transmittance of the electrochromic element is measured before the irradiation of the ultraviolet rays, and the second light transmittance of the electrochromic element is measured after the irradiation of the ultraviolet rays, and the light transmittance change rate is a value obtained by dividing the difference between the first light transmittance and the second light transmittance by the first light transmittance.

The above ultraviolet ray may be light radiated from a UVA 340 ultraviolet lamp. The UVA 340 ultraviolet lamp may be a fluorescent lamp that emits light with a spectrum having a maximum peak of about 340 nm. The UVA 340 ultraviolet lamp may have an emission spectrum as illustrated in FIG. 7.

The above light transmittance change rate (△TR) can be expressed by the following equation 1.

[Formula 1]

△TR = (T1 - T2) / T1

Here, T1 is the initial light transmittance of the electrochromic element, and T2 is the light transmittance of the electrochromic element after the ultraviolet ray is irradiated to the electrochromic part through the first substrate (100) at an intensity of about 7.5 W/㎡ for 1 hour.

The light transmittance change rate of the electrochromic device according to the embodiment may be less than about 0.25. The light transmittance change rate of the electrochromic device according to the embodiment may be from 0 to about 0.30. The light transmittance change rate of the electrochromic device according to the embodiment may be from 0 to about 0.25. The light transmittance change rate of the electrochromic device according to the embodiment may be from about 0.01 to about 0.20. The light transmittance change rate of the electrochromic device according to the embodiment may be from about 0.02 to about 0.18. The light transmittance change rate of the electrochromic device according to the embodiment may be from about 0.03 to about 0.15.

The light transmittance of the electrochromic element according to the embodiment can be from about 45% to about 90%. The light transmittance of the electrochromic element according to the embodiment can be from about 50% to about 85%. The light transmittance of the electrochromic element according to the embodiment can be from about 60% to about 80%.

The light transmittance of the electrochromic device according to the embodiment after the ultraviolet ray is irradiated may be about 40% to about 80%. The light transmittance of the electrochromic device according to the embodiment after the ultraviolet ray is irradiated may be about 45% to about 80%. The light transmittance of the electrochromic device according to the embodiment after the ultraviolet ray is irradiated may be about 50% to about 70%.

The electrochromic element according to the embodiment has the light transmittance change rate as described above. Accordingly, the electrochromic element according to the embodiment can reduce the change in transmittance caused by external sunlight, etc.

That is, since the electrochromic element according to the embodiment can reduce the transmittance deviation due to external sunlight, the target transmittance at the time of on-off can be easily controlled.

The electrochromic device according to the embodiment may have haze.

The above haze may refer to the haze of an electrochromic device according to an embodiment in a state where it is not photochromic or electrochromic.

The haze of the electrochromic device according to the embodiment may be less than about 5%. The haze of the electrochromic device according to the embodiment may be less than about 4%. The haze of the electrochromic device according to the embodiment may be less than about 3%. The haze of the electrochromic device according to the embodiment may be less than about 2%.

An electrochromic device according to an embodiment may have a haze change.

The above haze change can be measured by the following measurement method 2.

[Measurement Method 2]

Before the ultraviolet irradiation, the first haze of the electrochromic element according to the embodiment is measured, and after the ultraviolet irradiation, the second haze of the electrochromic element according to the embodiment is measured, and the haze change is a value obtained by subtracting the first haze from the second haze.

The haze change of the electrochromic device according to the embodiment may be less than 5.5%. The haze change of the electrochromic device according to the embodiment may be less than 5%. The haze change of the electrochromic device according to the embodiment may be less than 4%. The haze change of the electrochromic device according to the embodiment may be less than 3%. The haze change of the electrochromic device according to the embodiment may be less than 2%.

In the electrochromic device according to an embodiment, the haze after irradiating the ultraviolet ray may be less than about 6%. In the electrochromic device according to an embodiment, the haze after irradiating the ultraviolet ray may be less than about 5%. In the electrochromic device according to an embodiment, the haze after irradiating the ultraviolet ray may be less than about 4%. In the electrochromic device according to an embodiment, the haze after irradiating the ultraviolet ray may be less than about 3%.

The above light transmittance may be total light transmittance. The above light transmittance may be light transmittance in a wavelength range of about 380 nm to about 780 nm.

The above light transmittance and the above haze can be measured by ASTM D1003.

An electrochromic device according to an embodiment may have L*, a*, and b*.

The L* of the electrochromic device according to the embodiment may be from about 70 to about 100. The L* of the electrochromic device according to the embodiment may be from about 80 to about 100. The L* of the electrochromic device according to the embodiment may be from about 91 to about 100. The L* may be measured in a state where the electrochromic device according to the embodiment is not photochromic and/or electrochromic.

An electrochromic device according to an embodiment may have an L* change.

The above L* change can be measured by the following measurement method 3.

[Measurement Method 3]

Before the ultraviolet irradiation, the first L* of the electrochromic element according to the embodiment is measured, and after the ultraviolet irradiation, the second L* of the electrochromic element according to the embodiment is measured, and the change in L* is the absolute value of the value obtained by subtracting the first L* from the second L*.

The above L* change can be expressed by the following equation 2.

[Formula 2]

L* change = │2nd L* - 1st L*│

The L* change of the electrochromic device according to the embodiment may be less than 7. The L* change of the electrochromic device according to the embodiment may be less than 6. The L* change of the electrochromic device according to the embodiment may be less than 5. The L* change of the electrochromic device according to the embodiment may be less than 4.

In the electrochromic device according to the embodiment, L* after irradiation with the ultraviolet ray may be from about 70 to about 95. In the electrochromic device according to the embodiment, L* after irradiation with the ultraviolet ray may be from about 76 to about 94.

The a* of the electrochromic device according to the embodiment may be from -3 to 2. The a* of the electrochromic device according to the embodiment may be from -2.5 to 1.5. The a* of the electrochromic device according to the embodiment may be from -2 to 1. The a* may be measured in a state where the electrochromic device according to the embodiment is not photochromic and/or electrochromic.

An electrochromic device according to an embodiment may have an a* change.

The above a* change can be measured by the following measurement method 4.

[Measurement Method 4]

Before the ultraviolet irradiation, the first a* of the electrochromic element according to the embodiment is measured, and after the ultraviolet irradiation, the second a* of the electrochromic element according to the embodiment is measured, and the a* change is a value obtained by subtracting the first a* from the second a*.

The a* change of the electrochromic device according to the embodiment can be expressed by the following mathematical formula 3.

[Formula 3]

a* change = │2nd a* - 1st a*│

The a* change of the electrochromic device according to the embodiment may be less than 6. The a* change of the electrochromic device according to the embodiment may be less than 5. The a* change of the electrochromic device according to the embodiment may be less than 2. The a* change of the electrochromic device according to the embodiment may be less than 3. The a* change of the electrochromic device according to the embodiment may be less than 1.8. The a* change of the electrochromic device according to the embodiment may be less than 1.6. The a* change of the electrochromic device according to the embodiment may be less than 1.5.

In the electrochromic device according to the embodiment, a* after irradiation with the ultraviolet ray may be from about -5 to about 0. In the electrochromic device according to the embodiment, a* after irradiation with the ultraviolet ray may be from about -4.5 to about 0.

The b* of the electrochromic device according to the embodiment may be from 0 to 4. The b* of the electrochromic device according to the embodiment may be from 0.1 to 3.5. The b* of the electrochromic device according to the embodiment may be from 0.5 to 3. The b* may be measured in a state where the electrochromic device according to the embodiment is not photochromic and/or electrochromic.

An electrochromic device according to an embodiment may have a b* change.

The above b* change can be measured by the following measurement method 5.

[Measurement Method 5]

Before the ultraviolet irradiation, the first b* of the electrochromic element according to the embodiment is measured, and after the ultraviolet irradiation, the second b* of the electrochromic element according to the embodiment is measured, and the change in b* is a value obtained by subtracting the first b* from the second b*.

The above b* change can be calculated using the following equation 4.

[Formula 4]

b* change = │2nd b* - 1st b*│

The b* change of the electrochromic device according to the embodiment may be less than 10. The b* change of the electrochromic device according to the embodiment may be less than 8. The b* change of the electrochromic device according to the embodiment may be less than 7. The b* change of the electrochromic device according to the embodiment may be less than 2.8. The b* change of the electrochromic device according to the embodiment may be less than 2.6. The b* change of the electrochromic device according to the embodiment may be less than 2.5.

The b* after the ultraviolet ray is irradiated to the electrochromic device according to the embodiment may be from about -5 to about 3. The b* after the ultraviolet ray is irradiated to the electrochromic device according to the embodiment may be from about -4.5 to about 2.

The above L*, a* and b* can be measured by a colorimeter.

The electrochromic element according to the embodiment can have the haze change as described above. In addition, the electrochromic element according to the embodiment can have the L* change, the a* change, and the b* change.

Accordingly, the electrochromic element according to the embodiment can reduce changes in appearance due to external sunlight. Accordingly, the electrochromic element according to the embodiment can have a consistent appearance even when the external environment changes.

Since the electrochromic element according to the embodiment effectively blocks external ultraviolet rays, it can effectively protect the internal electrochromic part (11) from external ultraviolet rays.

Accordingly, the electrochromic element according to the embodiment can prevent electrons from being generated in the first discoloration layer when external ultraviolet rays are incident. Accordingly, the electrochromic element according to the embodiment can prevent some discoloration due to external ultraviolet rays.

Therefore, the electrochromic element according to the embodiment can have uniform optical characteristics regardless of external environments such as ultraviolet rays contained in sunlight.

Accordingly, the electrochromic element according to the embodiment is driven to have constant optical characteristics. In addition, since the electrochromic element according to the embodiment has constant driving characteristics, it can be driven with a constant driving voltage.

Accordingly, the electrochromic element according to the embodiment can be driven with a constant driving voltage and thus can have improved durability.

Fig. 8 is a drawing illustrating a window device (1) according to an embodiment.

Referring to FIG. 8, a window device (1) according to an embodiment includes an electrochromic element (10), a frame (20), windows (31, 32, 33), a plug-in component (40), and a power supply (50).

The frame (20) may be composed of one or more pieces. For example, the frame (20) may be composed of one or more materials, such as vinyl, PVC, aluminum (Al), steel, or fiberglass. The frame (20) fixes the windows (31, 32, 33) and seals the space between the windows (31, 32, 33). In addition,

The frame (20) may hold or include pieces of foam or other material. The frame (20) includes a spacer, which may be positioned between adjacent windows (31, 32, 33). Additionally, the spacer, together with an adhesive sealant, may hermetically seal the space between the windows (31, 32, 33).

The above windows (31, 32, 33) are fixed to the frame (20). The above windows (31, 32, 33) may be glass panes. The above windows (31, 32, 33) may be conventional silicon oxide (SOx)-based glass substrates such as soda lime glass or float glass composed of about 75% silica (SiO2) plus Na2O, CaO, and some minor additives. However, any material having suitable optical, electrical, thermal, and mechanical properties may be used. The above windows (31, 32, 33) may also include, for example, other glass materials, plastics and thermoplastics (e.g., poly(methyl methacrylate), polystyrene, polycarbonate, allyl diglycol carbonate, SAN (styrene acrylonitrile copolymer), poly(4-methyl-1-pentene), polyester, polyamide), or mirror materials. The above windows (31, 32, 33) may include tempered glass.

The above windows (31, 32, 33) may include a first window (31), a second window (32), and a third window (33). The first window (31) and the third window (33) may be positioned at the outermost side, and the second window (32) may be positioned between the first window (31) and the third window (33).

The electrochromic element (10) is placed between the first window (31) and the second window (32). The electrochromic element (10) can be laminated to the first window (31) and the second window (32).

The above electrochromic element (10) can be laminated to the first window (31) by the first polyvinyl butyral sheet. That is, the first polyvinyl butyral sheet is disposed on the first window (31) and the electrochromic element (10), and can be laminated to the first window (31) and the electrochromic element (10).

The above electrochromic element (10) can be laminated to the second window (32) by the second polyvinyl butyral sheet. That is, the second polyvinyl butyral sheet can be disposed on the second window (32) and the electrochromic element (10), and laminated to the second window (32) and the electrochromic element (10).

A space (60) may be formed between the second window (32) and the third window (33). The space may be filled with one or more gases such as argon (Ar), krypton (Kr), or xenon (Xn).

The above windows (31, 32, 33) can be glass pane sizes for residential or commercial window applications. The size of the glass pane can vary widely depending on the specific needs of the home or commercial business. In some embodiments, the windows (31, 32, 33) can be formed of architectural glass. Architectural glass is typically used in commercial buildings, but can also be used in residential buildings, typically, but not necessarily, to separate the indoor environment from the outdoor environment. In some embodiments, a suitable architectural glass substrate can be at least about 20 inches by about 20 inches, and can be much larger, for example, about 80 inches by about 120 inches, or larger. Architectural glass is typically at least about 2 millimeters (mm) thick and can be as thick as 6 mm or more.

In some embodiments, the windows (31, 32, 33) may have a thickness in the range of about 1 mm to about 10 mm.

In some embodiments, the windows (31, 32, 33) can be very thin and flexible, such as Gorilla Glass® or WillowTM Glass, each of which are commercially available from Corning, Inc. of New York, Corning, which glasses can be less than 0.3 mm or less than about 1 mm thick.

The above plug-in component (40) may include a first electrical input (41), a second electrical input (42), a third electrical input (43), a fourth electrical input (44) and a fifth electrical input (45).

Additionally, the power supply unit (50) includes a first power terminal (51) and a second power terminal (52).

The first electrical input (41) is electrically coupled to the first power terminal (51) via one or more wires or other electrical connections, components, or devices.

The first electrical input (41) may include a pin, a socket, or other electrical connector or conductor. In addition, the first electrical input (41) may be electrically connected to the electrochromic element (10) via a first bus bar (not shown). The first bus bar may be electrically connected to the second transparent electrode (400).

The second electrical input (42) is electrically coupled to the second power terminal (52) via one or more wires or other electrical connections, components, or devices.

The second electrical input (42) may include a pin, a socket, or other electrical connector or conductor. Additionally, the second electrical input (42) may be electrically connected to the electrochromic element (10) via a second bus bar (not shown). The second bus bar may be electrically connected to the first transparent electrode (300).

The third electrical input (43) may be coupled to a device, system, or building ground.

The fourth electrical input (44) and the fifth electrical input (45) above can be used individually, for example, for communication between a controller or microcontroller controlling the Windows device (1) and a network controller.

The power supply unit (50) supplies power to the electrochromic element (10) through the plug-in component (40). In addition, the power supply unit (50) is controlled by the external controller to supply power of a certain waveform to the electrochromic element (10).

In addition, the features, structures, effects, etc. described in the embodiments above are included in at least one embodiment of the present invention, and are not necessarily limited to only one embodiment. Furthermore, the features, structures, effects, etc. exemplified in each embodiment can be combined or modified and implemented in other embodiments by a person having ordinary knowledge in the field to which the embodiments belong. Therefore, the contents related to such combinations and modifications should be interpreted as being included in the scope of the present invention.

Although the above has been described with reference to examples, these are merely examples and do not limit the present invention. Those skilled in the art will appreciate that various modifications and applications not exemplified above are possible without departing from the essential characteristics of the present invention. For example, each component specifically shown in the examples can be modified and implemented. In addition, differences related to such modifications and applications should be interpreted as being included in the scope of the present invention defined in the appended claims.

Manufacturing example

ITO Film: Hansung Industrial Co., Ltd., HI150-ABE-125A-AB

Tungsten Oxide Powder: Adcro Co., Ltd., ELACO-W

Nickel Oxide Powder: Adcro Co., Ltd., ELACO-P

Gel polymer electrolyte composition

About 39 parts by weight of dipentaerythritol hexaacrylate (DPHA), about 80 parts by weight of ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [BMI-TFSI], and about 1 part by weight of diethoxyacetophenone (DEAP) were mixed, and LiBF4 (Li+ concentration: 1 mol/L) was added to prepare a gel polymer electrolyte composition.

Photocurable resin composition

A composition totaling 200 parts by weight, consisting of 60 parts by weight of EB-1290 from SK Cytec, 40 parts by weight of M340 (pentaerythritol triacrylate) from Miwon Speciality, 50 parts by weight of methyl ethyl ketone, 30 parts by weight of toluene, and 20 parts by weight of isopropyl alcohol, was stirred with a high-speed stirrer, and then an ultraviolet absorber (TinUVin 479) and a photoinitiator (Igacure 819) were mixed with the composition shown in Table 1 below to prepare a photocurable resin composition.

Example 1

In the first ITO film, the photocurable resin composition was coated with a thickness of about 5 ㎛ on the surface opposite to the surface on which the ITO layer was arranged. Thereafter, the coated photocurable resin composition was dried at about 80° C. for about 2 minutes, and then cured in a nitrogen atmosphere with a light amount of about 500 mJ in a high-pressure mercury lamp for about 5 minutes, thereby forming an ultraviolet ray blocking layer.

Thereafter, about 10 parts by weight of tungsten oxide powder, about 1 part by weight of TEOS, and about 90 parts by weight of ethanol were uniformly mixed to prepare a first discoloration material composition. The first discoloration material composition was coated on a first ITO film to a thickness of about 25 μm, and a first discoloration layer having a thickness of about 600 nm was formed by a sol-gel reaction at a temperature of about 110° C. for about 5 minutes. Accordingly, a first laminate including the first discoloration layer was formed.

About 11 parts by weight of nickel oxide powder, about 1 part by weight of TEOS, and about 89 parts by weight of ethanol were uniformly mixed to produce a second chromic material composition. The second chromic material composition was coated on a second ITO film to a thickness of about 40 μm, and a second laminate including a second chromic layer having a thickness of 1200 nm was produced by a sol-gel reaction at a temperature of about 120° C. for about 5 minutes. The gel polymer electrolyte composition was coated on the first chromic layer to a thickness of about 100 μm, the second ITO film having the second chromic layer formed thereon was laminated on the coated gel polymer electrolyte composition, and the coated gel polymer electrolyte composition was cured by UV light. Thereafter, the laminate was left at room temperature for about 14 hours to be aged. Accordingly, an electrochromic element according to an embodiment was manufactured.

Examples 2 to 4 and comparative examples

As shown in Table 1 below, the ultraviolet absorbent and photoinitiator were applied to form the ultraviolet blocking layer.

division UV absorber,
Content
(weight) Photoinitiator,
Content
(weight) Example 1 TinUVin 479, 3 3 Example 2 TinUVin 479, 6 5 Example 3 TinUVin 400, 6 5 Example 4 TinUVin 400, 10 5 Example 5 TinUVin 1130, 10 3 Comparative example - -

Evaluation example

1. QUV Test

According to an embodiment, an electrochromic device was continuously irradiated with ultraviolet light from a UVA 340 ultraviolet lamp at an intensity of about 0.75 W/㎡ for about 1 hour. The ultraviolet light was incident on the inside through the ultraviolet blocking layer.

2. Light transmittance

In the examples and manufacturing examples, in the electrochromic device, the transmittance before and after the ultraviolet irradiation are measured as total light transmittance in a wavelength range of about 380 nm to about 780 nm by a solar spectrum meter (EDTM, SS2450).

3. Haze

In the electrochromic devices manufactured in the examples and manufacturing examples, the haze before and after the ultraviolet irradiation are measured by (Konica-Minolta, CM-5).

4. Color value

In the electrochromic devices manufactured in the examples and manufacturing examples, the color values (L*, a* and b*) before the ultraviolet irradiation and the color values after the ultraviolet irradiation are measured by a spectrophotometer (Konica-Minolta, CM-5).

5. Charge and discharge test

In the electrochromic devices manufactured in the Examples and Comparative Examples, the (-) electrode of a charge/discharge tester (Won-A Tech, WBCS_D70714K1) is connected to a bus bar attached to tungsten oxide and the (+) electrode is connected to a bus bar attached to nickel oxide while being exposed to ultraviolet rays in a solar simulator. Thereafter, when a predetermined voltage is applied to reach a sufficiently high discoloration transmittance, each voltage is connected in reverse by the internal electrical deformation of the charge/discharge tester so that the (+) voltage is applied to the bus bar connected to tungsten oxide and the (-) voltage is applied to the bus bar connected to nickel oxide, and when a sufficiently low discoloration transmittance is reached, this is considered one cycle. The charge/discharge test is conducted by continuously repeating the cycle and measuring the transmittance and charge/discharge amount, and the number of times the discoloration range does not decrease after a certain cycle operation and the charge/discharge amount is maintained at 80% or more is measured.

As shown in Table 2 below, in the electrochromic devices according to the examples and comparative examples, the first optical transmittance, the second optical transmittance, the first haze, and the second haze were measured.

division 1st light transmittance
(%) Second light transmittance
(%) 1st Haze
(%) 2nd Haze
(%) Example 1 65 57 2.35 4.01 Example 2 67 59 2.44 1.83 Example 3 69 63 1.56 2.82 Example 4 65 60 1.89 3.35 Example 5 68 63 1.08 4.2 Comparative example 69 51 1.98 6.95

As shown in Table 3 below, color values and charge/discharge cycles were measured in electrochromic devices according to examples and comparative examples.

division 1st L* 2nd L* 1st a* 2nd a* 1st b* 2nd b* Recharge and discharge recovery
Example 1 90.54 89.9 0.54 -4.3 2.1 -3.5 8000 Example 2 91.5 90.2 0.35 -2.8 2.25 0.89 11000 Example 3 84.6 80.8 -1.81 -5.2 1.80 -3.4 20000 Example 4 87.13 79.9 -1.80 -5.63 1.7 -2.2 15000 Example 5 91.34 90.5 -1.85 -1.5 1.9 0.16 20000 Comparative example 93.33 84.19 0.67 -6.7 1.6 -4.41 3000

As described in Table 2 and Table 3 above, the electrochromic devices according to the examples had high light resistance to external ultraviolet rays.

First substrate (100)
Second substrate (200)
1st transparent electrode (300)
Second transparent electrode (400)
First discoloration layer (500)
Second discoloration layer (600)
Electrolyte layer (700)
UV protection layer (800)

Claims (11)

First substrate;
a second substrate disposed on the first substrate; and
An electrochromic member disposed between the first substrate and the second substrate;
The change in light transmittance measured by the following measurement method is less than 0.25,
An electrochromic device having a haze change of less than 5.5% as measured by the following measuring method.
[measurement method]
Through the first substrate, the electrochromic part is irradiated with ultraviolet light from a UVA 340 ultraviolet lamp at an intensity of 7.5 W/㎡ for 1 hour, the first light transmittance of the electrochromic element is measured before the irradiation with the ultraviolet light, the second light transmittance of the electrochromic element is measured after the irradiation with the ultraviolet light, and the light transmittance change rate is a value obtained by dividing the difference between the first light transmittance and the second light transmittance by the first light transmittance.
[measurement method]
Before the ultraviolet irradiation, the first haze of the electrochromic element according to the embodiment is measured, and after the ultraviolet irradiation, the second haze of the electrochromic element according to the embodiment is measured, and the haze change is a value obtained by subtracting the first haze from the second haze. delete An electrochromic device in accordance with claim 1, wherein the L* change measured by the measuring method described below is less than 9.
[measurement method]
Before the ultraviolet irradiation, the first L* of the electrochromic element is measured, and after the ultraviolet irradiation, the second L* of the electrochromic element is measured, and the change in L* is the absolute value of the value obtained by subtracting the first L* from the second L*. An electrochromic device in accordance with claim 3, wherein the change in a* measured by the following measuring method is less than 5.
[measurement method]
Before the ultraviolet irradiation, the first a* of the electrochromic element is measured, and after the ultraviolet irradiation, the second a* of the electrochromic element is measured, and the change in a* is the absolute value of the value obtained by subtracting the first a* from the second a*. An electrochromic device in accordance with claim 4, wherein the change in b* measured by the following measuring method is less than 10.
[measurement method]
Before the ultraviolet irradiation, the first b* of the electrochromic element is measured, and after the ultraviolet irradiation, the second b* of the electrochromic element is measured, and the change in b* is the absolute value of the value obtained by subtracting the first b* from the second b*. In paragraph 1,
Including an ultraviolet ray blocking layer provided on the first substrate,
The above ultraviolet ray blocking layer is an electrochromic element having a transmittance of 10% or less for ultraviolet rays of 340 nm. In claim 6, the ultraviolet ray blocking layer is an electrochromic device including at least one ultraviolet ray absorbent selected from the group consisting of a benzophenone-based ultraviolet ray absorbent, a benzoxazinone-based ultraviolet ray absorbent, a benzotriazole-based ultraviolet ray absorbent, and a triazine-based ultraviolet ray absorbent. An electrochromic element in the first aspect, wherein the first light transmittance is 50% to 85%, and the first haze is 0.1% to 5%. An electrochromic device in claim 5, wherein the first L* is 80 to 100, the first a* is -2 to 1.5, and the first b* is 0.5 to 4. An electrochromic element in claim 6, wherein the ultraviolet ray blocking layer is disposed between the first substrate and the electrochromic portion. frame;
a window mounted on the above frame; and
Including an electrochromic element arranged in the above window,
The above electrochromic element
First substrate;
A second substrate disposed on the first substrate;
Including an electrochromic member disposed between the first substrate and the second substrate,
The change in light transmittance measured by the following measurement method is less than 0.25,
A window device having a haze change of less than 5.5% as measured by the following measurement method.
[measurement method]
Through the first substrate, the electrochromic part is irradiated with ultraviolet light from a UVA 340 ultraviolet lamp at an intensity of 7.5 W/㎡ for 1 hour, the first light transmittance of the electrochromic element is measured before the irradiation with the ultraviolet light, the second light transmittance of the electrochromic element is measured after the irradiation with the ultraviolet light, and the light transmittance change rate is a value obtained by dividing the difference between the first light transmittance and the second light transmittance by the first light transmittance.
[measurement method]
Before the ultraviolet irradiation, the first haze of the electrochromic element according to the embodiment is measured, and after the ultraviolet irradiation, the second haze of the electrochromic element according to the embodiment is measured, and the haze change is a value obtained by subtracting the first haze from the second haze.