CN1315980C - Compound as electrochromic material and electrochromic module - Google Patents
Compound as electrochromic material and electrochromic module Download PDFInfo
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- CN1315980C CN1315980C CNB2004100462469A CN200410046246A CN1315980C CN 1315980 C CN1315980 C CN 1315980C CN B2004100462469 A CNB2004100462469 A CN B2004100462469A CN 200410046246 A CN200410046246 A CN 200410046246A CN 1315980 C CN1315980 C CN 1315980C
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- electrochromic
- compound
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- electrochromic window
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Abstract
The present invention relates to a compound as an electrochromic material. The compound has a structure disclosed in the following formula (I). The compound has the function of reduction discoloration. The compound is especially suitable for being used as a reduction discoloration material of the electrochromic material. When the compound is used as the reduction discoloration material of the electrochromic material, under the condition that ultraviolet absorbent is not added, the damage of the electrochromic material, which is caused by irradiation of ultraviolet rays, can be avoided, and a formed electrochromic component can keep good antiglare effect. The electrochromic component comprises a first transparent base material and a second transparent base material, wherein at least one of the first transparent base material and the second transparent base material is formed with a conductive thin film on the opposite side of the other party's surface, and the electrochromic material is arranged between the first transparent base material and the second transparent base material, and the electrochromic material comprises the compound disclosed in the formula (I). Therefore, through the efficacy of the compound, the electrochromic component can be used for manufacturing an automatic antiglare rear view mirror and an automatic shading plate used in a vehicle.
Description
Technical field
The invention relates to a kind of compound and electrochromic window assemblies as electrochromic material, particularly a kind of compound with reduction colour change function as electrochromic material, and use the made electrochromic window assemblies of this compound.
Background technology
The electrochromism phenomenon is meant the reversible color change that material follows transfer transport to cause.By the signal (for example applying voltage) of input, the electrochromism assembly can change transparency continuously.Owing to electrochromic window assemblies has the characteristic that influence by voltage changes reflectivity and penetration coefficient, be usually used in making the commodity such as rear vision mirror, color-changing solar glasses, skylight, sun visor of automobile, especially for automatic glareproof mirror and the automatic tinted shade of making automobile.
When driving night, the driver is in the environment of dark, and eye pupil is in open state as the shutter of photographic camera, so that offer the more optical signal of optic nerve.In this state, driver's eyes can produce the reaction of extreme sensitivity for emergent light.Usually, the automotive rear-view specular reflectance is from overtaking other vehicles or the headlight light of back vehicle and the head lamp light of sending a car previously, can make the driver produce the dizzy situation of vision, thereby cause visual performance moment of driver to be lowered rapidly, therefore increase the reaction times of driver for the place ahead obstacle.All nighttime driving persons are no matter sex, age or eye color all are subjected to the influence of this effect.A kind of rear vision mirror and tinted shade for overcoming this problem, developing with anti-dizzy function.
This rear vision mirror and tinted shade promptly are to utilize electrochromic window assemblies to have influence by voltage and the characteristic that changes reflectivity and penetration coefficient, when driving night, make its deepening by applying voltage, reduce the rear vision mirror reflection from overtaking other vehicles or the headlight light of back vehicle and the headlight light of sending a car previously and the dizzy situation of driver's vision that causes.
When driving in the daytime, the driver except doing not feel like oneself, can allow eye pupil be in minimum state, so that stopped strong light for reflection or point-blank dazzle.Under this situation, when the driver enters tunnel or the dim insufficient place of surrounding environment light from the environment that sunlight reflected or direct projection light are arranged, the pupil of driver's eyes can't amplify in real time so that provide to be looked to feeling neural more optical signal, allow driver's the visual performance reduce rapidly, thereby increased the driver and become reaction times when visible for the place ahead obstacle in moment.All nighttime driving persons are no matter sex, age or eye color all are subjected to the influence of this effect.A kind of tinted shade for overcoming this problem, developing with anti-dazzle function.
This tinted shade promptly is to utilize electrochromic window assemblies to have influence by voltage and the characteristic that changes reflectivity and penetration coefficient, when driving in the daytime, make its deepening by applying voltage, reduce the light that reflects or directly inject driver's eyes, to improve the dizzy situation of driver's vision.
At present, in this electrochromic window assemblies, mostly be to use happy brilliant preparation such as (benzyl viologen) the compound electrochromic solutions of methyl prestige happy brilliant (methylviologen), heptyl prestige happy brilliant (heptyl viologen), phenyl prestige happy brilliant (phenyl viologen) and phenmethyl prestige, be used as the off-color material of electrochromic window assemblies again.Yet this electrochromic window assemblies is quite responsive for light usually, and UV-light particularly is used to make that to be subjected to the automobile rearview mirror effect that UV-light tans by the sun for a long time bad.Therefore, need the extra UV light absorber of adding, avoid off-color material to be subjected to ultraviolet high energy radiation and destroyed.
Employed now UV light absorber belongs to organic compound mostly, has molecular absorption band in relevant wavelength, and can not absorb in visible spectrum range, but these compounds usually must be dissolved in the electrochromic solutions with high density.Because the restriction of solubleness often causes this UV light absorber validity deficiency.Therefore, still need a kind ofly can not be subjected to ultraviolet high energy radiation and suffer the destructive electrochromic material.
Summary of the invention
Main purpose of the present invention is to provide a kind of compound with reduction colour change function.
Another object of the present invention is to provide a kind of compound as electrochromic material.
Another purpose of the present invention is to provide a kind of UV light absorber of need not adding can avoid ultraviolet energy to destroy the electrochromic window assemblies of electrochromic material.
A further object of the present invention is to provide a kind of electrochromic window assemblies that is used to make automatic glareproof mirror.
Another purpose of the present invention is to provide a kind of electrochromic window assemblies that is used to make automatic anti-dazzle tinted shade.
For reaching above-mentioned and other purpose, the invention provides a kind of compound as electrochromic material, this compound has the structure shown in the following formula (I):
Because this compound has the function of reduction variable color, be particularly suitable as the reduction off-color material of electrochromic material.On the other hand, when using this compound to make electrochromic window assemblies as electrochromic material, do not adding under the situation of UV light absorber, this electrochromic material can not make formed electrochromic window assemblies can keep excellent antiglare effect because of ultraviolet irradiation is destroyed.
This electrochromic window assemblies comprises first transparent substrate and second transparent substrate, at least one of this first and second transparent substrate is to be formed with conductive film in the opposite side, and dispose electrochromic material between this first and second transparent substrate, wherein this electrochromic material comprises the compound shown in the formula (I), and then can apply to make employed automatic glareproof mirror of automobile and automatic tinted shade by means of its effect.
In sum, the invention provides a kind of compound with reduction colour change function, it also can be used as electrochromic material.The present invention also provides a kind of UV light absorber of need not adding can avoid ultraviolet energy to destroy the electrochromic window assemblies of electrochromic material, and this variable color assembly can be used for making automatic glareproof mirror and automatic anti-dazzle tinted shade.
Description of drawings
Fig. 1 is the preparation flow synoptic diagram of electrochromic window assemblies of the present invention;
Fig. 2 is that the structure of electrochromic window assemblies of the present invention is graphic;
Fig. 3 is that the structure of electrochromic window assemblies of the present invention is graphic; And
Fig. 4 is to use the schematic circuit of the pilot circuit of electrochromic window assemblies made glareproof mirror of the present invention.
Embodiment
Below be by particular specific embodiment explanation embodiments of the present invention.In specific embodiments of the invention, compound shown in the formula (I) is by 4,4 '-dipyridyl and methyl (4-brooethyl) benzoic ether, under the condition of adding cyanogen methane, react, the aqueous solution that then adds LiBF4 carries out ion-exchange, changes dibromide into a tetrafluoro borate and forms.
In the electrochromic window assemblies of the present invention, comprise first transparent substrate and second transparent substrate, the at least a of this first and second transparent substrate is to be formed with conductive film in the opposite side, and dispose electrochromic material between this first and second transparent substrate, wherein this electrochromic material comprises the compound shown in the formula (I).
Electrochromic window assemblies with the making glareproof mirror is an example, uses glass preferable as the transparent substrate in the electrochromic window assemblies.As shown in Figure 1, this first glass coating 1 and second glass coating 2 are to form conductive film (for example, tin indium oxide (ITO)) as conductive electrode layer 3, to be connected to impressed voltage in the opposite side; Under some particular case, also can only form conductive film as conductive electrode layer 3 in the opposite side of first glass coating 1 or second glass coating 2.This conductive electrode layer 3 can be formed on this glass coating by various appropriate means, for example the method for vacuum evaporation or sputter.
Then, as shown in Figure 1, by Resins, epoxy viscose glue 10, with conductive electrode layer 3 mode in opposite directions fit this first glass coating 1 and second glass coating 2, the gluing width of this Resins, epoxy viscose glue 10 is preferable with 2 to 3 millimeters.Usually, the Resins, epoxy viscose glue 10 of this first glass coating 1 and second glass coating 2 is used for fitting, be mixed with about 0.1 to the 0.2 millimeter glass sphere of 1.5 to 3% particle diameters as separation material, can produce certain spacing after this first glass coating 1 and this second glass coating 2 are fitted.
On the other hand, after this first glass coating 1 is fitted with this second glass coating 2, be in 100 to 150 ℃ baking oven, to toast, last about 1 to 2 hour, after treating that Resins, epoxy viscose glue 10 solidifies, can electrochromic solutions be injected this first glass coating 1 and this second glass coating 2 formed assembly chamber after fitting via the filling orifice of prior reservation, form electrochromic layer 4 as shown in Figure 2.
Be used for making the process implementing example of the electrochromic window assemblies of glareproof mirror in preparation, the offside that this first glass coating 1 is formed with conductive electrode layer is formed with reflecting layer 5.The material in this reflecting layer 5 can be selected from aluminium, silver, and the cohort that constituted such as chromium.For the personnel that have the knack of art technology, can select suitable mode according to circumstances for use, for example the mode of vacuum evaporation or sputter forms this reflecting layer 5 at this first glass coating 1.
In this specific embodiment, this electrochromic solutions comprises oxidation stain material, reduction off-color material, macromolecular material and solvent.Compound shown in the formula of the present invention (I) has the function of reduction variable color, be particularly suitable as and reduce off-color material in the electrochromic material, (for example cooperate suitable oxidation stain material, Fc (ferrocence)), macromolecular material (for example, polymethacrylate) and solvent (for example, propylene carbonate) promptly can be formulated into electrochromic solutions.Employed oxidation stain material, macromolecular material and solvent are all had the knack of this operator and are known in this electrochromic solutions, can select for use as required, so no longer illustrate at this.
Electrochromic window assemblies structure of the present invention also can be removed reflecting layer 5 shown in Figure 2 as shown in Figure 3, and its structure also comprises this first glass coating 6 and second glass coating 7, and the conductive electrode layer 8 and electrochromic layer 9 that are positioned at 6,7 of this glass coatings.
In addition, when the off-color material in the electrochromic layer of this electrochromic window assemblies is in oxidation state, the driving voltage that is applied can pass through conductive electrode layer, make the off-color material electron gain and reduction reaction takes place, make off-color material change into and go back ortho states, make that oxidation state is that colourless electrochromic material changes the colored materials of going back ortho states into by oxidation state.After the driving voltage that is applied disappeared, off-color material promptly transformed back into oxidation state and becomes again colourless from going back ortho states.The variable color amplitude of off-color material is also according to the voltage strength of being bestowed and different.By this characteristic, this electrochromic window assemblies can be applied to make glareproof mirror.
Generally speaking, glareproof mirror is made up of electrochromic window assemblies, pilot circuit (as shown in Figure 4) and shell mechanism.Because when this glareproof mirror can be according to running car, the light power that front car light throwed of back car was adjusted variable color intensity, make that the driver is unlikely to cause vision dizzy too by force because of the brightness of the front car light of back car, influence traffic safety.Simultaneously, this electrochromic window assemblies is to use the compound shown in the formula of the present invention (I) as electrochromic material; Therefore, do not need additionally to add UV light absorber, can avoid electrochromic material to be damaged because of uviolizing.
Below by specific embodiment, further describe characteristics of the present invention and effect.But this implementation detail only is used to illustrate characteristics of the present invention but not is used to limit to category of the present invention.
Embodiment
Preparation example 1
Respectively with 4 of 1.7 grams (0.01 mole), 4 '-methyl (4-brooethyl) benzoic ethers of dipyridyl and 5 grams (0.02 mole) are added in 250 milliliters the round-bottomed flask, the cyanogen methane that adds 30 milliliters, utilize agitator to stir, be heated to 85 ℃ and under this temperature, react, last 5 hours.Can produce yellow solid gradually in the reaction process, filter after question response finishes, isolate 3 gram yellow solid product (1, two (4-methoxycarbonyl) phenmethyls-4,4 of 1-'-the dipyridyl dibromide), productive rate about 60%.
Prepared yellow solid product inserted in 250 milliliters the round-bottomed flask, add water and heat and make its dissolving, add the LiBF4 aqueous solution that water is prepared again, and be cooled to 10 ℃, produce 2 gram white crystals things 1, two (4-methoxycarbonyl) phenmethyls-4,4 of 1-'-dipyridyl a tetrafluoro borate, i.e. compound shown in the formula (I).
Embodiment 1
According to the component content of tabulating down in 1, the preparation electrochromic solutions.
Table 1
| Composition | Content (gram) |
| 1, two (4-methoxycarbonyl) phenmethyls-4 of 1-, 4 '-dipyridyl a tetrafluoro borate | 1 |
| Ferrocence | 1 |
| PMMA | 5 |
| Propylene carbonate | 100 |
PMMA: polymethylmethacrylate
Test case 1
Use two length and width respectively be 26 centimeters and 6 centimeters, thickness be 1.8 centimeters transparent glass as the base material of electrochromic window assemblies, the surface of each transparent glass is coated with indium tin oxide layer, it is silver coated that wherein a slice transparent glass is coated with the offside of indium tin oxide layer.Utilize Resins, epoxy viscose glue (mix 3% particle diameter of having an appointment in this Resins, epoxy mucilage materials be 0.2 millimeter glass sphere),, stay next filling orifice with indium tin oxide layer mode in opposite directions two transparent glasses of fitting.Under 150 ℃ of temperature, toasted 1.5 hours, solidify this Resins, epoxy viscose glue, form the electrochromic window assemblies work in-process.
Above-mentioned electrochromic solutions is injected the electrochromic window assemblies work in-process, make electrochromic window assemblies.Under 25 ℃ condition, measure the reflectivity and the variable color speed of this electrochromic window assemblies, the result is embedded in table 2.
Table 2
| Project | The result |
| Variable color front-reflection rate | 71.2％ |
| Variable color back reflection rate | 8.5％ |
| Variable color speed (reducing to 15%) from 65% | 2 seconds |
| Variable color speed (rising to 65%) from 15% | 6 seconds |
| Variable color front-reflection rate (xenon lamp exposed to the sun according to 500 hours) | 68％ |
| Variable color back reflection rate (xenon lamp exposed to the sun according to 500 hours) | 9.4％ |
| Variable color front-reflection rate (DC1.1V loop test 30000 times) | 65％ |
| Variable color back reflection rate (DC1.1V loop test 30000 times) | 9.1％ |
Test case 2
Use two length and width respectively be 26 centimeters and 6 centimeters, thickness be 1.8 centimeters transparent glass as the base material of electrochromic window assemblies, the surface of each transparent glass is coated with indium tin oxide layer.Utilize Resins, epoxy viscose glue (mix 3% particle diameter of having an appointment in this Resins, epoxy mucilage materials be 0.2 millimeter glass sphere),, stay next filling orifice with indium tin oxide layer mode in opposite directions two transparent glasses of fitting.Under 150 ℃ temperature, toasted 1.5 hours, solidify this Resins, epoxy viscose glue, form the electrochromic window assemblies work in-process.
Above-mentioned electrochromic solutions is injected the electrochromic window assemblies work in-process, make electrochromic window assemblies.Under 25 ℃ condition, measure the penetration coefficient and the variable color speed of this electrochromic window assemblies, the result is embedded in table 3.
Table 3
| Project | The result |
| Penetration coefficient before the variable color | 75.3％ |
| Penetration coefficient after the variable color | 14.4％ |
| Variable color speed (reducing to 30%) from 65% | 2 seconds |
| Variable color speed (rising to 65%) from 30% | 6 seconds |
| Penetration coefficient before the variable color (xenon lamp exposed to the sun according to 500 hours) | 72％ |
| Penetration coefficient after the variable color (xenon lamp exposed to the sun according to 500 hours) | 12.6％ |
| Penetration coefficient (DC1.1V loop test 30000 times) before the variable color | 71.2％ |
| Penetration coefficient after the variable color (DC1.1V loop test 30000 times) | 12.2％ |
Claims (10)
1. the compound as electrochromic material is characterized in that, this compound has the structure shown in the following formula (I):
2. electrochromic window assemblies, it is characterized in that, this variable color assembly comprises first transparent substrate and second transparent substrate, at least a in this first and second transparent substrate is to form conductive film in the opposite side, and dispose electrochromic material between this first and second transparent substrate, wherein this electrochromic material comprises compound as claimed in claim 1.
3. electrochromic window assemblies as claimed in claim 2 is characterized in that this transparent substrate is a glass.
4. electrochromic window assemblies as claimed in claim 2 is characterized in that the opposite side of this first and second transparent substrate all is formed with conductive film.
5. electrochromic window assemblies as claimed in claim 2 is characterized in that this conductive film is a tin indium oxide.
6. electrochromic window assemblies as claimed in claim 2 is characterized in that this electrochromic material also comprises oxidation stain material, macromolecular material and solvent.
7. electrochromic window assemblies as claimed in claim 2 is characterized in that, the offside that this first transparent substrate is formed with conductive film is formed with the reflecting layer.
8. electrochromic window assemblies as claimed in claim 7 is characterized in that the material in this reflecting layer is selected from the cohort that aluminium, silver and chromium are formed.
9. an automatic glareproof mirror is characterized in that, uses electrochromic window assemblies as claimed in claim 2.
10. an automatic tinted shade is characterized in that, uses electrochromic window assemblies as claimed in claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100462469A CN1315980C (en) | 2004-06-04 | 2004-06-04 | Compound as electrochromic material and electrochromic module |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100462469A CN1315980C (en) | 2004-06-04 | 2004-06-04 | Compound as electrochromic material and electrochromic module |
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| Publication Number | Publication Date |
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| CN1706908A CN1706908A (en) | 2005-12-14 |
| CN1315980C true CN1315980C (en) | 2007-05-16 |
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| CNB2004100462469A Expired - Fee Related CN1315980C (en) | 2004-06-04 | 2004-06-04 | Compound as electrochromic material and electrochromic module |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234505B (en) * | 2010-04-29 | 2014-01-01 | 比亚迪股份有限公司 | Electrochromic material and preparation method thereof, and anti-dazzling automobile rear-vision mirror |
| CN102862520A (en) * | 2012-09-25 | 2013-01-09 | 江苏亿成光电科技有限公司 | Automatic anti-dazzling rear-view mirror |
| CN102942517A (en) * | 2012-11-12 | 2013-02-27 | 西南大学 | Conjugated expanded viologen derivative as well as preparation method and application thereof |
| CN102911210A (en) * | 2012-11-19 | 2013-02-06 | 高金菊 | Viologen compound |
| CN102965096B (en) * | 2012-11-21 | 2015-03-04 | 中国科学技术大学 | Purpurine compound electrochromic material and electrochromic device thereof |
| CN103091906B (en) * | 2013-01-30 | 2016-12-28 | 北京京东方光电科技有限公司 | A kind of mask plate |
| CN106647090A (en) * | 2017-03-10 | 2017-05-10 | 合肥鑫晟光电科技有限公司 | Mask plate and manufacturing method thereof, as well as shading device and control method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4210390A (en) * | 1977-06-28 | 1980-07-01 | Dai Nippon Toryo Co., Ltd. | Electrochromic composition and electrochromic display device using same |
| JPH11183940A (en) * | 1997-12-19 | 1999-07-09 | Nippon Mitsubishi Oil Corp | Electrochromic element |
| JP2000194019A (en) * | 1998-12-28 | 2000-07-14 | Murakami Corp | Solution phase electrochromic element |
| US6154306A (en) * | 1993-02-26 | 2000-11-28 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices |
| CN1341232A (en) * | 1999-02-18 | 2002-03-20 | 日石三菱株式会社 | Electrochemical element |
-
2004
- 2004-06-04 CN CNB2004100462469A patent/CN1315980C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4210390A (en) * | 1977-06-28 | 1980-07-01 | Dai Nippon Toryo Co., Ltd. | Electrochromic composition and electrochromic display device using same |
| US6154306A (en) * | 1993-02-26 | 2000-11-28 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices |
| JPH11183940A (en) * | 1997-12-19 | 1999-07-09 | Nippon Mitsubishi Oil Corp | Electrochromic element |
| JP2000194019A (en) * | 1998-12-28 | 2000-07-14 | Murakami Corp | Solution phase electrochromic element |
| CN1341232A (en) * | 1999-02-18 | 2002-03-20 | 日石三菱株式会社 | Electrochemical element |
Non-Patent Citations (1)
| Title |
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| 电致变色材料及应用 张征林 等，电子元件与材料 1999 * |
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