KR20190065027A - Polymer electrolyte composition for electrochromic device, polymer electrolyte and electrochromic device using the same - Google Patents

Abstract

The present invention relates to a polymer electrolyte composition for an electrochromic device, and a polymer electrolyte and the electrochromic device using the same, wherein the polymer electrolyte composition for the electrochromic device comprises a polyester urethane (meth)acrylate, a linear monoalkyl (meth)acrylate, a metal salt, and a polymerization initiator. The polymer electrolyte composition for the electrochromic device is curable by light or heat, has excellent shear strength, peel strength, and electrochemical performance after curing, exhibits excellent color development and decolorization performance by comprising a polymer having improved physical strength and optical performance, and has excellent storage stability, thermal stability and electrochemical stability.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer electrolyte composition for an electrochromic device, a polymer electrolyte using the polymer electrolyte, and an electrochromic device using the polymer electrolyte.

The present invention relates to a polymer electrolyte composition for an electrochromic device, and a polymer electrolyte and an electrochromic device using the polymer electrolyte composition.

BACKGROUND ART Electrochromic devices are devices that change the light transmission characteristics by utilizing the principle that the electric oxidation-reduction reaction proceeds according to the application of the electric field to change the color of the electrochromic material. This is widely used not only for display devices such as mobile phones, camcorders, notebooks, but also for automobile room mirrors and window smart windows.

1, the electrochromic device generally includes first and second electrodes 10 and 20 formed with transparent electroconductive layers 12 and 22 on a substrate 11 and 21 to which an electric field is applied, The electrochromic material layer 31 and 32 are laminated on the conductive layers 12 and 22 and are changed in color by the applied electric current. The electrolyte 50 for ion conduction and the sealing material 40 for sealing the electrolyte layer 50, .

As such an electrolyte 50, a liquid electrolyte and a polymer electrolyte are used. Liquid electrolytes have the advantage of good ionic conductivity, but they are disadvantageous in that the organic solvent is volatilized and depleted, there is a liquid leakage problem in manufacturing the device, the decolorization rate is slow, and the organic matter is easily decomposed by repeated coloring-decoloring.

On the other hand, unlike a liquid electrolyte, a polymer electrolyte is environmentally friendly because it does not have problems such as leakage of liquid, and it is possible to make a thin film and a film form, thereby facilitating structural modification of a device in a desired form. However, the proton or lithium ion diffusion reaction is slow and the ionic conductivity is low, which causes the electrochromic reaction to be delayed.

The object of the present invention is to provide a polymer electrolyte composition for an electrochromic device capable of improving ion conductivity at a level higher than that of a liquid electrolyte and having little influence on environmental factors (light and humidity) do.

Another object of the present invention is to provide a polymer electrolyte comprising the polymer electrolyte composition for an electrochromic device.

It is another object of the present invention to provide an electrochromic device comprising a cured product of the polymer electrolyte composition for an electrochromic device.

In order to solve the above-mentioned problems, the present invention relates to a polyester urethane (meth) acrylate; Linear monoalkyl (meth) acrylates; Metal salts; And a polymerization initiator. The present invention also provides a polymer electrolyte composition for an electrochromic device.

The present invention also provides a polymer electrolyte comprising a cured product of the polymer electrolyte composition for an electrochromic device.

The present invention also provides a plasma display panel comprising: a first electrode layer; A second electrode layer; An electrochromic layer disposed between the first electrode layer and the second electrode layer; And a polymer electrolyte layer disposed between the first electrode layer and the electrochromic layer, wherein the polymer electrolyte layer comprises a cured product of the polymer electrolyte composition for an electrochromic device.

The polymer electrolyte composition for an electrochromic device according to the present invention can exhibit excellent coloring and decolorizing performance because it contains a polymer which can be cured by light or heat, has excellent elastic restoring force and substrate adhesion, and has improved physical strength and optical performance . This makes it possible to increase the applicability in outdoor conditions such as buildings and vehicles by having durability against various external environments such as temperature, humidity and light.

1 is a view schematically showing the structure of a conventional electrochromic device.
2 is a graph showing FT-IR data of the polymer precursor prepared in Production Example 1 of the present invention.

Hereinafter, the present invention will be described in detail.

1. Polymer electrolyte composition

One aspect of the present invention provides a polymer electrolyte composition for an electrochromic device.

The polymer electrolyte composition includes a polyester urethane (meth) acrylate, a linear monoalkyl (meth) acrylate, a metal salt, and a polymerization initiator.

The polyester urethane (meth) acrylate is a compound capable of forming a polymer electrolyte by radical polymerization, and is a compound containing a polyester repeating unit and a urethane (meth) acrylate group. More specifically, the polyester urethane (meth) acrylate may include a main chain derived from a polyester polyol and a terminal group containing a urethane (meth) acrylic group.

The main chain derived from the polyester polyol may contain a repeating unit represented by the following formula (1).

[Chemical Formula 1]

(Wherein X, Y and Z are each independently a residue derived from a polyhydric alcohol having 2 to 6 OH groups at the terminal thereof, x, y and z are each independently an integer of 1 to 20, Each of l, m and n is independently an integer of 0 to 10,000, preferably an integer of 1,000 to 6,000.

The polyhydric alcohol may be at least one selected from the group consisting of ethylene glycol, polyethylene glycol, diethylene glycol, polydiethylene glycol, propylene glycol, polypropylene glycol, alkanediol, ethoxylated alkanediol, propoxylated alkanediol, trimethylolpropane, Trimethylol propane, propoxylated trimethylol propane, ditrimethylol propane, ethoxylated ditrimethylol propane, propoxylated ditrimethylol propane, pentaerythritol, ethoxylated pentaerythritol, propoxylated At least one selected from the group consisting of pentaerythritol, dipentaerythritol, ethoxylated dipentaerythritol, propoxylated dipentaerythritol, bisphenol A, ethoxylated bisphenol A, propoxylated bisphenol A, and combinations thereof And may contain one or more kinds of ethylene glycol And at least one member selected from the group consisting of diethylene glycol.

In Formula 1, X is a residue derived from ethylene glycol or polyethylene glycol, and Y may be a residue derived from diethylene glycol or polydiethylene glycol. In this case, l and m in Formula 2 are each independently an integer of 1 or more.

When the main chain of the polyester urethane (meth) acrylate contains both ethylene glycol and diethylene glycol as the polyhydric alcohol, it is possible to obtain a twisted linear (?) Structure by including an oxide structure of a heterogeneous type in the main group in the main chain structure linear. In this case, it is possible to obtain a large free volume compared to the general linear type polyester urethane (meth) acrylate, and it is possible to electron density unlike the polyester urethane (meth) acrylate containing only a single oxide structure The ionic conductivity of the polyester urethane (meth) acrylate can be improved. In addition, since it maintains a linear shape although it is a twisted linear shape, main properties such as shear strength and peel strength of the polyester urethane (meth) acrylate can be secured at the same time.

In the compound represented by the general formula (1), X is a residue derived from ethylene glycol or polyethylene glycol, and when Y is a residue derived from diethylene glycol or polydiethylene glycol, the ethylene glycol and diethylene glycol And may further comprise a residue derived from a third polyhydric alcohol other than the derived residue. If it further contains a residue derived from the third polyhydric alcohol, it is advantageous in securing ionic conductivity of the polymer.

Accordingly, in the above formula (1), Z is preferably selected from the group consisting of propylene glycol except for ethylene glycol and diethylene glycol, polypropylene glycol, alkane diol, ethoxylated alkanediol, propoxylated alkanediol propoxylated alkane diol), trimethylol propane, ethoxylated trimethylol propane, propoxylated trimethylol propane, ditrimethylol propane, ethoxylated ditrimethylol propane, propoxylated ditrimethylol propane, pentaerythritol , Ethoxylated pentaerythritol, propoxylated pentaerythritol, dipentaerythritol, ethoxylated dipentaerythritol, propoxylated dipentaerythritol, bisphenol A, ethoxylated bisphenol A, propoxylated bisphenol A A and any combination thereof. May be derived residues.

The terminal group containing the urethane (meth) acrylate group includes a group represented by the following general formula (2).

(2)

CH ₂ ═CR ₁ -C (═O) -O- (CR ₂ ) _p -NHC (═O) - *

(Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, and a combination thereof, and the p Is an integer of 1 to 10.)

In this case, * in the formula (2) represents a moiety connected to another formula.

The polyester urethane (meth) acrylate can be cured by light or heat as it contains the urethane (meth) acryl group, has excellent shear strength, peel strength and electrochemical performance after curing, and has physical strength and optical performance An improved polymer can be obtained.

The content of the polyester urethane (meth) acrylate may be 1 to 20 wt%, preferably 2 to 18 wt%, more preferably 3 to 10 wt%. If the content of the polyester urethane (meth) acrylate is less than 1% by weight, it may be difficult to realize the strength of the polymer electrolyte, and if it exceeds 10% by weight, the performance of the polymer electrolyte may deteriorate.

The polyester urethane (meth) acrylate may have a weight average molecular weight of 1,000 to 100,000, preferably 5,000 to 20,000. If the weight average molecular weight is less than 1,000, the performance of the electrolyte may be deteriorated as the crosslinking density increases. If the weight average molecular weight is more than 100,000, the crosslinking density may be insufficient.

The linear monoalkyl (meth) acrylate serves as a linker for connecting chains derived from the polyester urethane (meth) acrylate and can form a polymer electrolyte by curing (photo-curing or thermosetting) As the compound, it is possible that the alkyl moiety is a C ₄ to C ₁₀ substituted or unsubstituted alkyl moiety.

Specifically, the linear monoalkyl (meth) acrylate may include hexyl (meth) acrylate or heptyl (meth) acrylate.

The linear monoalkyl (meth) acrylate may comprise 0.5 to 5% by weight, preferably 0.5 to 3% by weight. If the content of the linear monoalkyl (meth) acrylate is less than 0.5% by weight, the electrolyte may be uncured to weaken the electrolyte. If the linear monoalkyl (meth) acrylate is more than 5% by weight, the crosslinking density may be increased.

In the polymer electrolyte composition of the present invention, the polymer may be prepared by polymerizing the polyester urethane (meth) acrylate and the linear monoalkyl (meth) acrylate. The polymerization initiator used herein may be a photopolymerization initiator or a thermal polymerization initiator . ≪ / RTI > Preferably a photopolymerization initiator.

The photopolymerization initiator may include at least one selected from the group consisting of alpha hydroxy ketone type, alpha amino ketone type, benzyldimethyl ketal, phenyl glyoxylate type, phosphine oxide type, and mixtures thereof.

The thermal polymerization initiator may include azobisisobutyronitrile, benzoyl peroxide, and the like.

The content of the polymerization initiator may be 0.01 to 5% by weight, preferably 0.1 to 2% by weight. When the content of the polymerization initiator is less than 0.01% by weight, polymerization of the polymer may not be smoothly performed. If the content of the initiator is more than 5% by weight, the initiator may remain in the resultant polymer electrolyte and adversely affect physical properties of the polymer electrolyte.

The metal salt is used to provide a metal ion to the polymer electrolyte composition. The metal salt is inserted or removed in the electrochromic material to change the oxidation number of the transition metal contained in the electrochromic material, thereby changing the optical property, .

As the metal salt, it is preferable to use an alkali metal salt. Specifically, a cation selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ and Cs ⁺ and a cation selected from the group consisting of F ^- , Cl ^- , Br ^- , I ^- , NO ₃ ^- , (CN) ₂ N ^- , BF ₄ ^{- _{ClO 4 -, RSO 3 -,}} RCOO - (R is an alkyl group or a phenyl group having a carbon number of ^{_{1-9), PF 6 -, AsF}} 6 -, SbF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF _{^{3 -, (CF 3) 4}} PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, (CF 3 SO 3 -) 2, (CF 2 CF 2 SO 3 -) 2, (C _{2 F 5 SO 2) 2 N} -, (CF 3 SO 3) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO _{2) 2 CH-, (SF 5} ) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 COO -, C 3 F 7 COO -, CF 3 SO ₃ ^- and C ₄ F ₉ SO ₃ ^- .

The content of the metal salt may be 10 to 35% by weight, preferably 20 to 30% by weight. If the content of the metal salt is less than 10% by weight, the ionic conductivity of the polymer electrolyte may be very poor, and if the content of the metal salt exceeds 35% by weight, the solubility of the polymer electrolyte may be decreased.

The metal salt may be dissolved in an organic solvent and included in the electrolyte composition. As such an organic solvent, an organic solvent used in the art can be used without limitation.

For example, at least one non-aqueous organic solvent selected from the group consisting of a carbonate-based, ester-based, ether-based, and ketone-based solvent.

Examples of the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate (MEC) EC), propylene carbonate (PC), and butylene carbonate (BC).

Examples of the ester solvent include methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, dimethylacetate, methyl propionate methyl propionate, ethyl propionate,? -butyrolactone, decanolide,? -valerolactone, mevalonolactone, at least one selected from the group consisting of? -caprolactone,? -valerolactone, and? -caprolactone.

Examples of the ether solvent include dimethyl ether, diethyl ether, dibutyl ether, tetraglyme, 1,3-dioxolane, , 2-methyltetrahydrofuran, tetrahydrofuran, and the like may be included.

The ketone-based solvent may include cyclohexanone.

The content of the organic solvent in which the metal salt is dissolved accounts for most of the polymer electrolyte composition for an electrochromic device, and may be included as a balance with respect to the content of the components of the polymer electrolyte composition for electrochromic devices.

The polymer electrolyte composition of the present invention may further contain other additives such as antifoaming agents, suppressing agents and leveling agents which may be contained in the electrolyte for an electrochromic device in addition to the above-described components.

The polymer electrolyte composition can be produced by a conventional method used in the technical field of the present invention. For example, the polymer electrolyte may be prepared by a solution casting method or an in-situ crosslinking method.

When the solution casting method is used, the polymer electrolyte composition may be cast or coated to form a thin film, followed by evaporating the solvent to obtain a polymer electrolyte film. At this time, if a low boiling point solvent is employed, a solid polymer electrolyte is obtained, and if a solvent has a high boiling point, a gel polymer electrolyte can be obtained.

When the in-situ crosslinking method is used, the polymer electrolyte composition can be obtained by injecting the polymer electrolyte composition into the electrochromic device in a non-electrolytic state prepared in advance and curing (crosslinking) by applying heat or light. At this time, it is also possible to provide a solid polymer electrolyte or a gel polymer electrolyte by controlling the kind or degree of crosslinking of the solvent considering the boiling point of the solvent.

The polymer electrolyte may have excellent light transmittance in the visible light region. In one example, the polymer electrolyte formed by applying and drying the polymer electrolyte to a thickness of 150 μm after drying the polymer electrolyte may have a light transmittance of about 90% or more in the visible light region. And the polymer electrolyte can exhibit low haze with excellent light transmittance.

For example, the polymer electrolyte formed in the same condition as that for measuring the light transmittance may exhibit a haze of 2% or less. Therefore, the polymer electrolyte can be applied to an electrolyte for a transparent display.

2. Polymer electrolytes and electrochromic devices

Another aspect of the present invention provides a polymer electrolyte comprising a cured product of a polymer electrolyte composition for an electrochromic device and an electrochromic device comprising the polymer electrolyte.

The electrochromic device of the present invention includes a first electrode layer, a second electrode layer, an electrochromic layer disposed between the first electrode layer and the second electrode layer, and a polymer electrolyte layer disposed between the first electrode layer and the electrochromic layer . At this time, the polymer electrolyte layer may be a cured product of the polymer electrolyte composition for an electrochromic device.

The first electrode layer and the second electrode layer may have a structure in which a transparent conductive layer is formed on a substrate.

The substrate and the transparent conductive layer are not particularly limited as long as they are well known in the art. Examples of the conductive material for forming the transparent conductive layer include ITO (indium doped tin oxide), ATO (antimony doped tin oxide), FTO (fluorine doped tin oxide ), Indium doped zinc oxide (IZO), and ZnO. A transparent conductive layer can be formed on the substrate by depositing a conductive material by a known method such as sputtering, electron beam evaporation, chemical vapor deposition, or sol-gel coating.

Examples of the electrochromic material for forming the electrochromic layer include WO ₃ , Ir (OH) _x , MoO ₃ , V ₂ O ₅ , TiO ₂ , NiO _x , LiNiO _x , Li ₂ NiO _x , Organic electrochromic materials such as polypyrrole, polyaniline, polyazulene, polypyridine, polyindole, polycarbazole, polyazine, and polythiophene, or organic coloring materials such as viologen, anthraquinone and phenothiazine , Or a mixture thereof.

The method of laminating the electrochromic material on the electrode layer is not particularly limited as long as the thin film can be formed at a constant height from the basal plane along the surface profile. For example, a vacuum deposition method such as sputtering can be used.

Of the electrochromic materials, WO ₃ is a substance that is colored by a reduction reaction, and NiO is a substance that is colored by an oxidation reaction.

The electrochemical mechanism by which electrochromism occurs in an electrochromic device containing such an inorganic metal oxide is explained as shown in the following reaction formula (1). Specifically, when a voltage is applied to the electrochromic device, the proton (H ⁺ ) or lithium ion (Li ⁺ ) contained in the electrolyte is inserted or eliminated as an electrochromic material depending on the polarity of the electric current. The change in the oxidation number of the transition metal contained in the electrochromic material changes the optical characteristic of the electrochromic material itself, for example, the transmittance (color).

[Reaction Scheme 1]

WO ₃ (transparent) + xe + _x M↔M _x WO ₃ (deep blue)

(In the above scheme, M is a proton or an alkali metal cation such as Li ^& lt ^{; + &} gt ;.)

The electrochromic device thus constructed may be manufactured according to a conventional method known in the art. For example, the first electrode layer and the second electrode layer may be fabricated, a first electrode layer may be formed between the first electrode layer and the second electrode layer, Injecting the polymer electrolyte composition for a discoloring element and sealing the polymer electrolyte composition; and polymerizing the injected polymer electrolyte composition to form a polymer electrolyte.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Manufacturing example ]

In a vacuum distillation reactor, 45 mol of adipic acid, 30 mol of ethylene glycol, 20 mol of diethylene glycol, and 5 mol of trimethylol propane were charged, and then the temperature was gradually raised to about 200 캜. While maintaining the above temperature, a small amount of catalyst was added, and after one hour of reaction, the vacuum process proceeded for 12 hours to prepare a polyester polyol.

The OH value (value) of the polyester polyol thus prepared and the NCO content of isocyanatoethyl methacrylate were calculated at appropriate ratios, and the resulting mixture was reacted at 80 ° C for 3 hours in the presence of a catalyst to obtain a polyester precursor polyester urethane Metha) acrylate.

FT-IR data of the polyester urethane (meth) acrylate prepared above are shown in FIG. 2, and the weight average molecular weight is 10,000.

[ Example  And Comparative Example ]

(1) Polymer electrolyte composition

Polymer electrolyte compositions were prepared with the compositions shown in Table 1 below.

(2) The electrochromic device

An ITO transparent conductive layer was deposited on the glass substrate to a thickness of 150 nm, and a 200 nm thick WO ₃ electrochromic material thin film was formed thereon by a sputtering method to prepare a working electrode. Further, a counter electrode having a NiO thin film with a thickness of 300 nm was manufactured in the same manner as the working electrode. Except for a part of the rim of the working electrode and the counter electrode (electrolyte injection hole), a UV sealant was used to produce an electrochromic device intermediate without electrolyte. The polymer electrolyte composition prepared in (1) was injected into the prepared intermediate, sealed with a UV sealing material, and then irradiated with light for 1 minute in an ultraviolet (UV) exposure apparatus to prepare an electrochromic device by in situ polymerization.

Composition component Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polyester urethane acrylate
(Mw, g / mol)
(weight%) PEUA (10,000)
(4) PEUA (10,000)
(8) PEUA (10,000)
(17) PEUA (10,000)
(2.5) PEUA
(10,000)
(4) PEUA
(10,000)
(4) PEUA
(10,000)
(30) PEUA
(10,000)
(4) PEUA
(10,000)
(4) Monomolecular acrylate
(Mw, g / mol)
(weight%) HA
(156)
(One) HA
(156)
(2) HA
(156)
(3) HA
(156)
(2.5) HA
(156)
(One) HA
(156)
(One) - 2-EHA
(184)
(One) DPHA
(578)
(One) Li-salt
(Mw, g / mol)
(weight%) LiTFSI
(287)
(26.8) LiTFSI
(287)
(25.8) LiTFSI
(287)
(22.8) LiTFSI
(287)
(52.8) LiClO4
(106)
(8.8) LiTFSI
(287)
(26) LiTFSI
(287)
(29.8) LiTFSI
(287)
(26.8) LiTFSI
(287)
(26.8) Solvent (wt%) PC
(68) PC
(64) PC
(57) PC
(68) PC
(86) PC
(68) PC
(40) PC
(68) PC
(68) Initiator (wt%) Ketone
(0.2) Ketone
(0.2) Ketone
(0.2) Ketone
(0.2) Ketone
(0.2) Phosphine oxide
(One) Ketone
(0.2) Ketone
(0.2) Ketone
(0.2) Polymer content 5 wt% 10 wt% 20 wt% 5 wt% 5 wt% 5 wt% 30 wt% 5 wt% 5 wt% PEUA: Polyester urethane acrylate
HA: hexyl acrylate
2-EHA: 2-ethylhexyl acrylate
DPHA: dipentaerythritol hexaacrylate
PC: propylene carbonate
Phosphine oxide: diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide
Initiator: Oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone

[ Experimental Example ]

The physical properties of the polymer electrolyte composition and the electrochromic device prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2.

1) Hardening degree: The degree of hardening was calculated by FT-IR measurement of electrolytes, and the conversion rate of C = C group to C-C group was calculated and the vertical falling hardness was measured by microTXA equipment.

2) Elastic restoring force: Measured with a microTXA instrument from Chemilab. Electrolyte samples were made in 50 * 50 * 0.5mm size and load was applied to 2mm spherical tip of TXA equipment.

3) Base adhesive strength: A 0.1 mm-thick electrolyte was filled between bare glass, and after curing, adhesion was judged when glass was opened.

4) Discoloration and Decolorization Transmittance: An EC cell was fabricated by filling the electrolyte between the EC substrates with a thickness of 0.1 mm, followed by UV curing. The transmittance of the visible light region (380 to 750 nm) was measured with the Spectrometer equipment under the discoloration / discoloration driving state by applying a voltage of about 0.8 to 1.5 V to the cell.

5) Evaluation of light resistance: Using a QVAB QUV equipment, a sample of 50 * 50 * 0.1 mm electrolyte was prepared, and the change of haze and b * values were compared using a Minolta spectrometer after 100 hours by ASTM method.

6) Accelerated humidity resistance evaluation: The optical properties were evaluated after 100h of 85% humidity / 85 ℃ condition using PCT (Pressure cooker test chamber) equipment.

Cell type Bare glass EC cell Evaluation items Degree of hardening Elastic resilience
(gf) Substrate adhesion Initial discoloration / decolorization transmittance After 50,000 cycles, the discoloration / decolorization transmittance Transmittance after 85/85 test After QUV
Δ b * After QUV
haze Example 1 Elastic gel 700 ok 2.3 / 81.4 4.6 / 80.1 2.8 / 81.0 0.1 0.1 Example 2 Elastic gel 600 ok 2.5 / 80.8 5.2 / 79.3 3.2 / 80.1 0.2 0.1 Example 3 Hard gel 250 ok 2.8 / 78.3 5.7 / 76.2 3.0 / 77.6 0.2 0.3 Example 4 Hard gel 200 ok 3.1 / 77.1 5.4 / 76.6 3.3 / 77.0 0.3 0.3 Example 5 Soft gel 150 x 4.8 / 75.1 7.2 / 73.6 5.3 / 74.3 0.4 0.7 Example 6 Elastic gel 700 ok 2.2 / 79.7 4.7 / 78.5 2.6 / 78.1 0.6 0.2 Comparative Example 1 Elastic gel 500 x 3.3 / 79.5 5.8 / 78.4 4.2 / 78.1 0.2 0.3 Comparative Example 2 Elastic gel 550 ok 2.4 / 79.7 4.3 / 77.5 3.2 / 78.3 0.3 0.5 Comparative Example 3 Hard gel 250 ok 3.4 / 78.4 6.3 / 76.8 4.7 / 78.1 0.5 0.4

Referring to Table 2, except for examples in which the lithium salt or the photoinitiator is changed in the examples including the polyester urethane (meth) acrylate and the linear monoalkyl (meth) acrylate (Examples 5 and 6) Moisture resistance, and optical properties after evaluation of QUV. On the other hand, in the case of the comparative examples not containing the linear monoalkyl (meth) acrylate, it was confirmed that the adherence of the base material was lowered and the change of the optical characteristics, especially the yellowishness and the haze after the QUV evaluation, were increased.

10: first electrode
11: substrate for first electrode
12: conductive layer for first electrode
20: Second electrode
21: substrate for second electrode
22: conductive layer for second electrode
31: Electrochromic material layer of the first electrode
32: Electrochromic material layer of the second electrode
40: Seal material
50: electrolyte

Claims (20)

Polyester urethane (meth) acrylate;
Linear monoalkyl (meth) acrylates;
Metal salts; And
A polymer electrolyte composition for an electrochromic device comprising a polymerization initiator. The method according to claim 1,
Wherein the polyester urethane (meth) acrylate comprises a main chain derived from a polyester polyol and a terminal group containing a urethane (meth) acrylate group. The method according to claim 1,
Wherein the main chain derived from the polyester polyol contains a repeating unit represented by the following general formula (1).
[Chemical Formula 1]

(Wherein X, Y and Z are each independently a residue derived from a polyhydric alcohol having 2 to 6 OH groups at the terminal thereof, x, y and z are each independently an integer of 1 to 20, Each of l, m and n is independently an integer of 0 to 10,000) The method of claim 3,
The polyhydric alcohol may be at least one selected from the group consisting of ethylene glycol, polyethylene glycol, diethylene glycol, polydiethylene glycol, propylene glycol, polypropylene glycol, alkanediol, ethoxylated alkanediol, propoxylated alkanediol, trimethylolpropane, Trimethylol propane, propoxylated trimethylol propane, ditrimethylol propane, ethoxylated ditrimethylol propane, propoxylated ditrimethylol propane, pentaerythritol, ethoxylated pentaerythritol, propoxylated At least one selected from the group consisting of pentaerythritol, dipentaerythritol, ethoxylated dipentaerythritol, propoxylated dipentaerythritol, bisphenol A, ethoxylated bisphenol A, propoxylated bisphenol A, and combinations thereof Wherein the electrochromic device comprises at least one electrochromic device Molecular electrolyte composition. The method of claim 3,
Wherein the polyhydric alcohol comprises at least one member selected from the group consisting of ethylene glycol and diethylene glycol. The method according to claim 1,
Wherein the terminal group containing the urethane (meth) acrylate group comprises a group represented by the following general formula (2).
(2)
CH ₂ ═CR ₁ -C (═O) -O- (CR ₂ ) _p -NHC (═O) - *
(Wherein R ₁ and R ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, and a combination thereof, and the p Is an integer of 1 to 10.) The method according to claim 1,
Wherein the polyester urethane (meth) acrylate has a weight average molecular weight of 1,000 to 100,000. The method according to claim 1,
Wherein the content of the polyester urethane (meth) acrylate is 1 to 20% by weight. The method according to claim 1,
Wherein the linear monoalkyl (meth) acrylate comprises an alkyl moiety wherein the alkyl moiety is a C ₄ to C ₁₀ substituted or unsubstituted alkyl moiety. The method according to claim 1,
Wherein said linear monoalkyl (meth) acrylate comprises hexyl (meth) acrylate or heptyl (meth) acrylate. The method according to claim 1,
Wherein the content of the linear monoalkyl (meth) acrylate is 0.5 to 5% by weight. The method according to claim 1,
Wherein the metal salt is selected from the group consisting of Li ⁺ , Na ⁺ , K ^+, and Cs ⁺ and a cation selected from the group consisting of F ^- , Cl ^- , Br ^- , I ^- , NO ₃ ^- , (CN) ₂ N ^- , BF ₄ ^{- _{ClO 4 -, RSO 3 -,}} RCOO - (R is an alkyl group or a phenyl group having a carbon number of ^{_{1-9), PF 6 -, AsF}} 6 -, SbF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF ^{_{3 -, (CF 3) 4}} PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, (CF 3 SO 3 -) 2, (CF 2 CF 2 SO 3 -) 2, (C _{2 F 5 SO 2) 2 N} -, (CF 3 SO 3) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO _{2) 2 CH-, (SF 5} ) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 COO -, C 3 F 7 COO -, CF 3 SO ₃ ^- and C ₄ F ₉ SO ₃ ^- . The method according to claim 1,
Wherein the content of the metal salt is 10 to 35% by weight. The method according to claim 1,
Wherein the polymerization initiator comprises a photopolymerization initiator or a thermal polymerization initiator. The method according to claim 1,
Wherein the polymerization initiator is a photopolymerization initiator that is at least one selected from the group consisting of alpha hydroxy ketone type, alpha amino ketone type, benzyl dimethyl ketal, phenyl glyoxylate type, phosphine oxide type, and mixtures thereof. Polymer electrolyte composition. The method according to claim 1,
Wherein the content of the polymerization initiator is 0.01 to 5% by weight based on the total weight of the polymer electrolyte composition. The method according to claim 1,
Wherein the polymer electrolyte composition further comprises at least one non-aqueous organic solvent selected from the group consisting of carbonate, ester, ether and ketone. 18. The method of claim 17,
The carbonate-based nonaqueous solvent may be selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate Wherein at least one selected from the group consisting of carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC) is contained. A polymer electrolyte comprising a cured product of the polymer electrolyte composition for an electrochromic device according to any one of claims 1 to 18. A first electrode layer;
A second electrode layer;
An electrochromic layer disposed between the first electrode layer and the second electrode layer; And
And a polymer electrolyte layer disposed between the first electrode layer and the electrochromic layer,
Wherein the polymer electrolyte layer contains a cured product of the polymer electrolyte composition for an electrochromic device according to any one of claims 1 to 18.

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