CN101334568A - Electrochromic mirror - Google Patents

Electrochromic mirror Download PDF

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Publication number
CN101334568A
CN101334568A CN 200810124993 CN200810124993A CN101334568A CN 101334568 A CN101334568 A CN 101334568A CN 200810124993 CN200810124993 CN 200810124993 CN 200810124993 A CN200810124993 A CN 200810124993A CN 101334568 A CN101334568 A CN 101334568A
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China
Prior art keywords
film
conductive reflecting
mirror
reflecting film
electrochromic
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CN 200810124993
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CN101334568B (en
Inventor
仲保纯一
服部正治
山口敦
斋藤永宏
石崎贵裕
高井治
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Nagoya University NUC
Tokai Rika Co Ltd
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Nagoya University NUC
Tokai Rika Co Ltd
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Priority claimed from JP2007167910A external-priority patent/JP5014893B2/en
Priority claimed from JP2007167913A external-priority patent/JP2009008750A/en
Priority claimed from JP2007167912A external-priority patent/JP2009008749A/en
Application filed by Nagoya University NUC, Tokai Rika Co Ltd filed Critical Nagoya University NUC
Publication of CN101334568A publication Critical patent/CN101334568A/en
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Publication of CN101334568B publication Critical patent/CN101334568B/en
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Abstract

An electrochromic mirror includes an electrochromic film, an electrically conductive reflective film formed at one thickness direction side of the electrochromic film, an electrically conductive film provided at one thickness direction side of the electrochromic film and at a side of the electrically conductive reflective film that is opposite from the electrochromic film, an electrolytic solution containing lithium ions and enclosed between the electrically conductive reflective film and the electrically conductive film, and a reduction reaction compensation unit. In the electrolytic solution, due to applying a voltage such that the electrically conductive film is made positive and electrically conductive reflective film is made negative, the lithium ions move toward the side of the electrochromic film and are provided to a reduction reaction of the electrochromic film. The reduction reaction compensation unit compensates the reduction reaction.

Description

EC mirror
Technical field
For example the present invention relates to be used for outside rear-view mirror of vehicle (rearview outer mirror) or inside rear-view mirror (rearview inner mirror) and can be by applying the EC mirror that voltage changes reflectivity.
Background technology
At United States Patent (USP) 3,844, in the instructions of No. 636 patents, a kind of EC mirror is disclosed, wherein, electrochromic film is colored owing to this electrochromic film carries out reduction reaction, thereby has reduced catoptrical transmitance, causes the reflection of light rate to reduce.
Summary of the invention
Consider above-mentioned situation and made the present invention, the invention provides a kind of EC mirror.
According to a scheme of the present invention, a kind of EC mirror is provided, described EC mirror comprises: electrochromic film, described electrochromic film is colored owing to carrying out reduction reaction; Conductive reflecting film with electric conductivity, described conductive reflecting film are formed on the side of thickness direction of described electrochromic film and the light that reflection has seen through described electrochromic film; Conducting film with electric conductivity, described conducting film are arranged on the side of thickness direction of described electrochromic film and a side opposite with described electrochromic film of described conductive reflecting film; Electrolytic solution, described electrolytic solution comprises lithium ion, and be encapsulated between described conductive reflecting film and the described conducting film, wherein, since apply voltage make described conducting film for just and described conductive reflecting film for bearing, so described lithium ion is towards described electrochromic film side shifting, and supply to the reduction reaction of described electrochromic film; With the reduction reaction compensating unit, described reduction reaction compensating unit by storage be in the electric charge that applies described voltage status or by with described electrolytic solution in negative ion carry out oxidation reaction, compensate described reduction reaction.
Description of drawings
To be elaborated to preferred implementation of the present invention based on the following drawings, wherein:
Fig. 1 is the sectional view of the overview of the formation of the EC mirror of demonstration first illustrative embodiments of the present invention;
Fig. 2 is for showing Li XWO 3In X and the curve map of the relation between the light reflectivity;
Fig. 3 is the thickness of demonstration electrochromic film 16 and the curve map of the relation between the reflectivity;
Fig. 4 is the sectional view of the overview of the formation of the EC mirror of demonstration second illustrative embodiments of the present invention;
Fig. 5 is the sectional view of the overview of the formation of the EC mirror of demonstration the 3rd illustrative embodiments of the present invention;
Fig. 6 is the sectional view of the overview of the formation of the EC mirror of demonstration the 4th illustrative embodiments of the present invention;
Fig. 7 is the diagrammatic cross-section that the major part of the EC mirror of the 4th illustrative embodiments of the present invention is amplified;
Fig. 8 for the ratio of the internal diameter size D that shows through hole and adjacent through hole distance between centers L with because the curve map of the relation between the minimizing ratio of the reflectivity of the EC mirror that the formation through hole causes;
Fig. 9 is the sectional view of the overview of the formation of the EC mirror of demonstration the 5th illustrative embodiments of the present invention;
Figure 10 is the diagrammatic cross-section that the major part of the EC mirror of the 5th illustrative embodiments of the present invention is amplified;
Figure 11 is the sectional view of the overview of the formation of the EC mirror of demonstration the 6th illustrative embodiments of the present invention;
Figure 12 is the diagrammatic cross-section that the major part of the EC mirror of the 6th illustrative embodiments of the present invention is amplified;
Figure 13 is for corresponding with Figure 12 and shown the sectional view of variation of the EC mirror of the 6th illustrative embodiments of the present invention;
Figure 14 is the sectional view of the overview of the formation of the EC mirror of demonstration the 7th illustrative embodiments of the present invention;
Figure 15 is the sectional view of the overview of the formation of the EC mirror of demonstration the 8th illustrative embodiments of the present invention;
Figure 16 is the sectional view of the overview of the formation of the EC mirror of demonstration the 9th illustrative embodiments of the present invention;
Figure 17 is the diagrammatic cross-section that the major part of the EC mirror of the 9th illustrative embodiments of the present invention is amplified;
Figure 18 is the sectional view of the overview of the formation of the EC mirror of demonstration the tenth illustrative embodiments of the present invention;
Figure 19 is the diagrammatic cross-section that the major part of the EC mirror of the tenth illustrative embodiments of the present invention is amplified;
Figure 20 is the sectional view of the overview of the formation of the EC mirror of demonstration the 11 illustrative embodiments of the present invention;
Figure 21 is the sectional view of the overview of the formation of the EC mirror of demonstration the 12 illustrative embodiments of the present invention; With
Figure 22 is the sectional view of the overview of the formation of the EC mirror of demonstration the 13 illustrative embodiments of the present invention.
Embodiment
The formation of＜the first illustrative embodiments 〉
In EC mirror, electrochromic film is colored owing to this electrochromic film carries out reduction reaction.In disclosed EC mirror in the instructions of 3,844, No. 636 patents of the U.S., graphite film stores negative ion, as the charge compensation of such reduction reaction.
But, fully painted because the anionic storage volume in such graphite film is little in order to make electrochromic film, must apply big voltage.When applying so big voltage, electrochromic film becomes and is easy to deterioration, and practicality reduces.In addition, voltage being applied in the formation of electrochromic film, when painted electrochromic film is decoloured, must apply opposite voltage by applying this big voltage.
Therefore, also can make fully painted EC mirror of electrochromic film even need not apply big voltage.
In Fig. 1, the formation of the EC mirror 10 of first illustrative embodiments of the present invention is shown in diagrammatic cross-section.
As shown in this figure, EC mirror 10 is provided with face side substrate 12.Face side substrate 12 is provided with the transparent base main body 14 that is formed by glass etc.Surface in a side of the Width (arrow W direction among Fig. 1) of this base main body 14 is formed with electrochromic film 16.Electrochromic film 16 is by for example tungstic acid (WO 3), molybdenum trioxide (MoO 3) or contain this hopcalite and form, especially, in this illustrative embodiments, electrochromic film 16 is formed by tungstic acid.
In the scope of 300nm～1000nm, especially, in this illustrative embodiments, the described thickness setting of electrochromic film 16 is 500nm to electrochromic film 16 along the thickness setting of the thickness direction of base main body 14.Surface in the side opposite with base main body 14 of electrochromic film 16 is formed with conductive reflecting film 18.Conductive reflecting film 18 has electric conductivity, by having gloss and can forming through the metal (for example, rhodium (Rh), ruthenium (Ru), palladium (Pd) or nickel (Ni) etc.) of lithium ion.In the scope of 30nm～200nm, especially, in this illustrative embodiments, the described thickness setting of conductive reflecting film 18 is 50nm to conductive reflecting film 18 along the thickness setting of the thickness direction of base main body 14.
In a side of the thickness direction of the face side substrate 12 of above-mentioned formation, thereby be provided with rear side substrate 24 towards face side substrate 12.Rear side substrate 24 is provided with the transparent base main body 26 that is formed by glass etc.Surface at the opposite side (being face side substrate 12 sides) of the thickness direction of this base main body 26 is formed with conducting film 28.Conducting film 28 is by such as chromium (Cr) or nickel metal, tin indium oxide (In such as (Ni) 2O 3: Sn, perhaps so-called " ITO "), tin oxide (SnO 2), fluorine-doped tin oxide (SnO 2: F) or zinc paste (ZnO 2) wait formation, perhaps the potpourri by these materials forms.
Surface in face side substrate 12 sides of conducting film 28 is formed with the carbon film 30 with electric conductivity.Carbon film 30 comprises as synthetic resin materials such as phenolics, polyimide resin or acryl resins as bonding agent.In addition, except that these bonding agents, carbon film 30 is also formed by the potpourri of graphite, carbon black and activated charcoal, especially, contains activated charcoal with the amount more than the 50 weight % in this potpourri.
Carbon film 30 is set at more than the 50 μ m along the gauge of the thickness direction of base main body 26, and in the carbon film 30 of above-mentioned formation, capacitance settings is 10mF/cm 2More than, perhaps the charge storage capacity when the voltage of 1.5V is set at 15mQ/cm 2More than.Especially, in this illustrative embodiments, capacitance settings is 20mF/cm 2, perhaps the charge storage capacity when the voltage of 1.5V is set at 30mQ/cm 2
Between the face side substrate 12 and rear side substrate 24 of above-mentioned formation, be formed with predetermined gap, and between the peripheral part of the peripheral part of face side substrate 12 and rear side substrate 24, seal by sealing material 32.Electrolytic solution 34 is encapsulated in the space that is surrounded by face side substrate 12, rear side substrate 24 and sealing material 32.Electrolytic solution 34 comprises the solvent that is formed by propylene carbonate, ethylene carbonate, carbonic acid fourth diester, diethyl carbonate, gamma-butyrolacton or dimethyl formamide etc. or formed by the potpourri of these materials, especially, in this illustrative embodiments, propylene carbonate is used as solvent.
Except that such solvent, electrolytic solution 34 also comprises lithium perchlorate (LiClO 4), lithium hexafluoro phosphate (LiPF 6), LiBF4 (LiBF 4), two (fluoroform sulphonyl) imide li (LiN (SO 2CF 3) 2), two (five fluorine second sulphonyl) imide li (LiN (SO 2C 2F 5) 2) or trifluoromethanesulfonic acid lithium (LiCF 3SO 3) wait or the potpourri of these materials as electrolyte, especially, in this illustrative embodiments, with lithium perchlorate as electrolyte.
In addition, the conducting film 28 of the EC mirror 10 of above-mentioned formation is connected to the switch 42 that constitutes loop 40.In switch 42, constitute and the positive pole of direct supply 44 with rated voltage of about 1.3V is connected to connected terminal when the ON state by on-vehicle battery etc.The negative pole of direct supply 44 is connected to conductive reflecting film 18.And the terminal that connects switch 42 when the OFF state is connected to conductive reflecting film 18, and connects without above-mentioned direct supply 44, and, when the OFF state, conducting film 28 and conductive reflecting film 18 short circuits.
The effect of＜the first illustrative embodiments and effect 〉
In the EC mirror 10 of above-mentioned formation, when the OFF of switch 42 state, electrochromic film 16 substantial transparent that becomes, therefore, from the light transmission base main body 14 and the electrochromic film 16 of the side incident opposite of base main body 14, and be reflected at conductive reflecting film 18 places with electrochromic film 16.In addition, the light transmission electrochromic film 16 and the base main body 14 that are reflected at conductive reflecting film 18 places, the result is in this illustrative embodiments of above-mentioned formation, and light reflectivity becomes about 55%.
On the other hand, when switch 42 switches to the ON state, passed the electronics (e that loop 40 moves to conductive reflecting film 18 sides -) enter in the electrochromic film 16, constitute the electrolytical lithium ion (Li of electrolytic solution 34 +) enter in the electrochromic film 16 through conductive reflecting film 18.As a result, in electrochromic film 16, the reduction reaction of following formula 1 taking place, is called the Li of the blueness of so-called tungsten bronze XWO 3Be formed in the electrochromic film 16.
Li ++ e -+ WO 3→ Li XWO 3(formula 1)
Because electrochromic film 16 is colored blue in this way, so electrochromic film 16 is reduced to about 7% for about 55% reflectivity before being colored.
In addition, when above-mentioned reduction reaction takes place after, electronics (e -) move to direct supply 44 sides from the carbon that constitutes carbon film 30, thus, constitute the negative ion (ClO of electrolytical lithium perchlorate 4 -) move to carbon film 30 sides.As a result, with respect to above-mentioned reduction reaction, taken place all as shown in the formula the compensatory reaction shown in 2.
ClO 4 -+ C-e -→ C +ClO 4 -(formula 2)
In Fig. 2, Li XWO 3In X and the relation between the light reflectivity shown in curve map.In this curve map, it should be noted that, the situation of X=0, promptly tungstic acid is transparent situation, is defined as 1.So shown in the curve map, more than X=0.15, locate, generally take place saturatedly, therefore,, in electrochromic film 16, reach fully painted at about X=0.15～0.2 place.
On the other hand, in Fig. 3, the thickness of electrochromic film 16 and the relation between the reflectivity are shown in curve map.It should be noted that in this curve map the reflectivity during no electrochromic film 16 is defined as 1.So shown in the curve map, because the thickness that reflectivity sharply reduces up to electrochromic film 16 becomes 300nm and saturated in the generation of 500nm place, so the thickness of electrochromic film 16 is preferably set to 300nm～500nm.
If Li XWO 3In the value of X be set in 0.15, the thickness d of electrochromic film 16 is set in 500nm, the bulk density ρ that constitutes the tungstic acid of electrochromic film 16 is set in 7.18g/cm 3, the emptying aperture degree P that constitutes the tungstic acid of electrochromic film 16 is set in 0.8, and Faraday constant F is set in 96485.3415Q/mol, and the molecular weight M of tungstic acid is set in 231.9mol, and with these substitution following formulas 3, then charge storage capacity Q becomes 17.92mQ/cm 2, and, be set in 1.3 and (be Q=17.92mQ/cm if apply voltage V with the result of formula 3 2) substitution following formula 4, then capacitor C becomes 13.79mF/cm 2
Q=(Xd ρ PF)/M (formula 3)
C=Q/V (formula 4)
In other words, in order to carry out painted reduction reaction fully in electrochromic film 16, it is necessary that the electric capacity of the charge storage capacity of following formula 3 gained and following formula 4 gained becomes.In this illustrative embodiments, carbon film 30 comprises activated charcoal.Activated charcoal is a porous, thereby surface area is bigger.Therefore, it has the ability that stores many negative ion and positive charge, so the electric capacity of carbon film 30 can be set in 20mF/cm 2, perhaps the charge storage capacity when the voltage of 1.5V can be set at 30mQ/cm 2
In this way, in this illustrative embodiments, electric capacity and charge storage capacity are all fully greater than the result of calculation in above-mentioned formula 3 and the formula 4.Therefore, in electrochromic film 16, can cause enough reduction reactions to take place, so as mentioned above, by switch 42 being switched to the ON state and applying voltage, electrochromic film 16 can obtain painted fully.
And carbon film 30 not only contains activated charcoal, also contains graphite and carbon ink, so carbon film 30 has been endowed sufficient electric conductivity, the reaction in the carbon film 30 can obtain quickening.
In addition, in this illustrative embodiments, when making electrochromic film 16 painted, the voltage that is applied can be low to moderate 1.3V.So, when switch 42 switched to OFF state and conductive reflecting film 18 and conducting film 28 short circuits, the backward reaction of following formula 1 and formula 2 took place, electrochromic film 16 decolours rapidly.
When the mirror main body of the inside rear-view mirror that is used for vehicle for example such as above-mentioned EC mirror 10 or outside rear-view mirror (peephole or fender mirror (fender mirror)) etc., in the daytime the time, thereby switch 42 can be remained on the OFF state and carry out backsight with high reflectance, when situations such as night, when the vehicle at rear is opened headlight, make electrochromic film 16 painted and reduction reflectivity by switch 42 being switched to the ON state, can reduce the reflected light of headlight, and reduce dazzle.
Next step will describe other illustrative embodiments of the present invention.It should be noted that, when each following illustrative embodiments is described, for with the illustrative embodiments that is illustrating before the illustrative embodiments that comprises first illustrative embodiments in substantially the same position, position, distribute identical Reference numeral, and omitted its detailed description.
The formation of＜the second illustrative embodiments 〉
In Fig. 4, the formation of the EC mirror 210 of second illustrative embodiments of the present invention is shown in diagrammatic cross-section.
As shown in this figure, EC mirror 210 is not provided with carbon film 30, the substitute is, and is provided with anionic reactive film 230 as the reduction reaction compensating unit.
Be formed on conducting film 28 face side substrate 12 sides the surface anionic reactive film 230 by such as polypyrrole, polyaniline, polyacetylene, polythiophene, poly-ly form to electric conductive polymer such as pyrene (polyparapyene) or poly-furans or such as redox polymerses such as polyvinyl ferrocene.For example, when with polypyrrole when the anionic reactive film 230, form by the pyrroles being dissolved in solvent and this being coated on the base main body 26.In addition, when with the polyvinyl ferrocene when the anionic reactive film 230, form by vinyl ferrocene being dissolved in solvent and this being coated on the base main body 26.The quality settings of anionic reactive film 230 is 0.012mg/cm 2More than.
The effect of＜the second illustrative embodiments and effect 〉
In the EC mirror 210 of above-mentioned formation, when the OFF of switch 42 state, electrochromic film 16 substantial transparent that becomes, therefore, from the light transmission base main body 14 and the electrochromic film 16 of the side incident opposite of base main body 14, and be reflected at conductive reflecting film 18 places with electrochromic film 16.In addition, the light transmission electrochromic film 16 and the base main body 14 that are reflected at conductive reflecting film 18 places, the result is in this illustrative embodiments of above-mentioned formation, and light reflectivity becomes about 55%.
On the other hand, when switch 42 switches to the ON state, passed the electronics (e that loop 40 moves to conductive reflecting film 18 sides -) enter in the electrochromic film 16, constitute the electrolytical lithium ion (Li of electrolytic solution 34 +) enter in the electrochromic film 16 through conductive reflecting film 18.As a result, in electrochromic film 16, the reduction reaction of following formula 1 taking place, is called the Li of the blueness of so-called tungsten bronze XWO 3Be formed in the electrochromic film 16.
Li ++ e -+ WO 3→ Li XWO 3(formula 1)
Because electrochromic film 16 is colored blue in this way, so electrochromic film 16 is reduced to about 7% for about 55% reflectivity before being colored.
In this EC mirror 210, when switching to the ON state owing to switch 42 reduction reaction of above-mentioned formula 1 takes place, constitute the oxidized and lotus that becomes positively charged of the electric conductive polymer of anionic reactive film 230 or redox polymers.As a result, constitute the negative ion (ClO of electrolytical lithium perchlorate 4 -) enter in the anionic reactive film 230 and set up charge balance.In this way, with respect to above-mentioned reduction reaction, if anionic reactive film 230 is formed by polypyrrole, all compensatory reactions as shown in the formula 5a take place then, and if anionic reactive film 230 is formed by the polyvinyl ferrocene, all compensatory reactions as shown in the formula 5b then take place.
ClO 4 -+ PPy-e -→ PPy +ClO 4 -(formula 5a)
ClO 4 -+ PVF-e -→ PVF +ClO 4 -(formula 5b)
It should be noted that PPy refers to polypyrrole among the formula 5a, PVF refers to the polyvinyl ferrocene among the formula 5b.
If Li XWO 3In the value of X be set in 0.15, the thickness d of electrochromic film 16 is set in 500nm, the bulk density ρ that constitutes the tungstic acid of electrochromic film 16 is set in 7.18g/cm 3, the emptying aperture degree P that constitutes the tungstic acid of electrochromic film 16 is set in 0.8, the molecular weight M of tungstic acid WBe set in 231.9mol, and with these substitution following formulas 6, then the reacting dose of tungstic acid (molal quantity) n becomes 1.86mM/cm 2
N=(Xd ρ P)/M W(formula 6)
In addition, the electric conductive polymer of the formation anionic reactive film 230 of the molal quantity identical with said n or redox polymers also must reactions.Therefore, when every monomer molecule amount Mp of electric conductive polymer used in the anionic reactive film 230 or redox polymers was set in 65.07g/mol and substitution following formula 7, quality m was 0.012mg/cm 2Electric conductive polymer or redox polymers become necessary.
M=nM P(formula 7)
In this illustrative embodiments, for anionic reactive film 230, m is set in 0.012mg/cm 2More than.Therefore, in electrochromic film 16, can cause enough reduction reactions to take place, so as mentioned above, by switch 42 being switched to the ON state and applying voltage, electrochromic film 16 can obtain painted fully.
In addition, in this illustrative embodiments, when making electrochromic film 16 painted, the voltage that is applied can be low to moderate 1.3V.So, when switch 42 switched to OFF state and conductive reflecting film 18 and conducting film 28 short circuits, the backward reaction of following formula 5a or formula 5b took place, electrochromic film 16 decolours rapidly.
When the mirror main body of the inside rear-view mirror that is used for vehicle for example such as above-mentioned EC mirror 210 or outside rear-view mirror (peephole or fender mirror) etc., in the daytime the time, thereby switch 42 can be remained on the OFF state and carry out backsight with high reflectance, when situations such as night, when the vehicle at rear is opened headlight, make electrochromic film 16 painted and reduction reflectivity by switch 42 being switched to the ON state, can reduce the reflected light of headlight, and reduce dazzle.
The formation of＜the three illustrative embodiments 〉
In Fig. 5, the formation of the EC mirror 310 of the 3rd illustrative embodiments of the present invention is shown in diagrammatic cross-section.
In EC mirror 310, conducting film 28 is formed by silver (Ag).In addition, as shown in this figure, compare, do not form carbon film 30, the substitute is, be formed with difficulty soluble salt film 330 in the surface of face side substrate 12 sides of conducting film 28 with first illustrative embodiments.Difficulty soluble salt film 330 is formed by silver chloride, bromine chloride or sulfur chloride cyanate etc., and especially, in this illustrative embodiments, difficulty soluble salt film 330 is formed by silver chloride.
The effect of＜the three illustrative embodiments and effect 〉
In this EC mirror 310, when the reduction reaction of above-mentioned formula 1 taking place in electrochromic film 16, shown in 8, constitute the negative ion (Cl of electrolytical lithium perchlorate because switch 42 switches to the ON state -) react with the silver (Ag) that constitutes conducting film 28, so silver chloride (AgCl) produces and separates out on the difficulty soluble salt film 330 that is formed by silver chloride.As a result, carried out and above-mentioned reduction reaction corresponding compensation.
Cl -+ Ag-e -→ AgCl (formula 8)
In this way, in this illustrative embodiments, owing in electrochromic film 16, compensatory reaction takes place reliably, so when making electrochromic film 16 painted, the voltage that is applied can be low to moderate 1.3V with respect to reduction reaction.So, when switch 42 switched to OFF state and conductive reflecting film 18 and conducting film 28 short circuits, the backward reaction of following formula 1 and formula 8 took place, electrochromic film 16 decolours rapidly.
When aforesaid EC mirror 310 is used for the mirror main body of the inside rear-view mirror of vehicle for example or outside rear-view mirror (peephole or fender mirror) etc., in the daytime the time, thereby switch 42 can be remained on the OFF state and carry out backsight with high reflectance, when situations such as night, when the vehicle at rear is opened headlight, make electrochromic film 16 painted and reduction reflectivity by switch 42 being switched to the ON state, can reduce the reflected light of headlight, and reduce dazzle.
The formation of＜the four illustrative embodiments 〉
In Fig. 6, the formation of the EC mirror 60 of the 4th illustrative embodiments of the present invention that its major part is exaggerated is shown in diagrammatic cross-section.
As shown in this figure, EC mirror 60 is not provided with conductive reflecting film 18, the substitute is, and is provided with conductive reflecting film 68.Conductive reflecting film 68 usefulness form with same thickness with conductive reflecting film 18 identical materials, but as shown in Figure 7, are formed with a plurality of fine through hole 70 that connects at its thickness direction in conductive reflecting film 68.The internal diameter of through hole 70 (diameter of interior perimembranous) dimension D is below the 20 μ m, and especially, in this illustrative embodiments, it is 5 μ m.And in conductive reflecting film 68, through hole 70 is to form irregular (at random) basically.But, to be configured to make the distance between centers L of adjacent through hole 70 be 10 μ m to through hole 70.
Through hole 70 forms by following manner: photomask (pattern of printing through hole 70 on the conductive reflecting film 68 that is coated with photoresist) is set, expose, remove then and through hole 70 corresponding photoresists, and dissolve conductive reflecting film 68 with etching liquid.
The effect of＜the four illustrative embodiments and effect 〉
In the EC mirror 60 of above-mentioned formation, owing in conductive reflecting film 68, be formed with through hole 70 as mentioned above, so when switch 42 switches to the ON state and applies voltage, owing to constitute the electrolytical lithium ion (Li of electrolytic solution 34 +) pass through hole 70 these facts, and do not forming the location lithium ion (Li of through hole 70 +) compare when seeing through conductive reflecting film 68, they enter in the electrochromic film 16 quickly.As a result, reduction reaction takes place rapidly in electrochromic film 16, whole electrochromic film 16 is by painted rapidly.
In addition, in this illustrative embodiments, because internal diameter (diameter of the interior perimembranous) dimension D of through hole 70 is set at 5 μ m (promptly 20 μ m are following), so through hole 70 can not directly be observed visually basically.So even when forming through hole 70, the light time of visual inspection EC mirror 60 places reflection can not produce factitious sensation yet.
Simultaneously, in Fig. 8, shown internal diameter (diameter of the interior perimembranous) dimension D of through hole 70 and adjacent through hole 70 distance between centers L ratio and owing to form relation between the minimizing ratio of reflectivity at EC mirror 60 places due to the through hole 70.In this illustrative embodiments, the distance between centers L of adjacent through hole 70 is set in 10 μ m because the internal diameter size D of through hole 70 is set in 5 μ m, so their ratio becomes 0.5.As a result, as shown in Figure 8, can guarantee to have 80% reflectivity when not forming through hole 70.In this way, be set at 0.5 by the ratio with the internal diameter size D of through hole 70 and the distance between centers L of adjacent through hole 70, although formed through hole 70 these facts, light can be reflected fully at conductive reflecting film 68 places.
In addition, in this illustrative embodiments, although the distance between centers L of adjacent through hole 70 is set in 10 μ m, it forms position irregular (at random).Therefore, the rule that does not produce the light of conductive reflecting film 68 places reflection is interfered.As a result, can make reflection image more clear.
It should be noted that, the formation of the EC mirror 60 of this illustrative embodiments is substantially the same with the formation of the EC mirror 10 of first illustrative embodiments, and difference is to be provided with the conductive reflecting film 68 that wherein is formed with through hole 70 and replaces conductive reflecting film 18 these facts.Therefore, EC mirror 60 has realized the effect identical with EC mirror 10 basically, and can obtain the effect identical with EC mirror 10.
It should be noted that this 4th illustrative embodiments is the variation of first to the 3rd illustrative embodiments.Used and be provided with carbon film 30 and describe as the EC mirror 60 of reduction reaction compensating unit.
But, illustrated being provided with in the EC mirror 210 of anionic reactive film 230 as the reduction reaction compensating unit can be provided with the conductive reflecting film 68 that wherein is formed with through hole 70 and replace conductive reflecting film 18 in second illustrative embodiments.So EC mirror 60 has realized the effect identical with EC mirror 210 basically, and can obtain the effect identical with EC mirror 210.
In addition, in the 3rd illustrative embodiments, in the illustrated EC mirror 310 that is provided with conducting film 28 that forms by silver and the difficulty soluble salt film 330 that constitutes the reduction reaction compensating unit, the conductive reflecting film 68 that wherein is formed with through hole 70 can be set replace conductive reflecting film 18.So EC mirror 60 has realized the effect identical with EC mirror 310 basically, and can obtain the effect identical with EC mirror 310.
The formation of＜the five illustrative embodiments 〉
Next step will describe the 5th illustrative embodiments of the present invention.
In Fig. 9, the formation of the EC mirror 80 of the 5th illustrative embodiments of the present invention is shown in diagrammatic cross-section.
As shown in this figure, EC mirror 80 is not provided with electrochromic film 16, the substitute is, and is provided with electrochromic film 86.Electrochromic film 86 still, as shown in figure 10, is formed with a plurality of fine through hole 92 that connects at its thickness direction by forming with identical thickness with electrochromic film 16 identical materials in electrochromic film 86.Through hole 92 communicates with through hole 70, and its internal diameter (diameter of interior perimembranous) dimension D is below the 20 μ m, especially, is set in 5 μ m in this illustrative embodiments.In addition, through hole 92 irregular basically (at random) forms in electrochromic film 86.But, the distance between centers L of adjacent through hole 92 is set in 10 μ m.
Through hole 92 forms by following manner: photomask (pattern of printing through hole 92 on the electrochromic film 86 that is coated with photoresist) is set, expose, remove then and through hole 92 corresponding photoresists, and dissolve electrochromic film 86 with etching liquid.
The effect of＜the five illustrative embodiments and effect 〉
In the EC mirror 80 of above-mentioned formation, in conductive reflecting film 68, be formed with through hole 70, in electrochromic film 86, be formed with through hole 92.So, when switch 42 switches to the ON state and applies voltage, at first, owing to constitute the electrolytical lithium ion (Li of electrolytic solution 34 +) pass through hole 70 these facts, so, and do not forming the location lithium ion (Li of through hole 70 +) compare when seeing through conductive reflecting film 68, they arrive electrochromic film 86 quickly.
In addition, the lithium ion that has arrived electrochromic film 86 enters through hole 92 and enters the electrochromic film 86 from the interior perimembranous of through hole 92.As a result, reduction reaction takes place more quickly in electrochromic film 86, whole electrochromic film 86 is by more promptly painted.
In addition, in this illustrative embodiments, because internal diameter (diameter of the interior perimembranous) dimension D of through hole 92 is set at 5 μ m (promptly 20 μ m are following), so through hole 92 can not directly be observed visually basically.So even when forming through hole 92, the light time of visual inspection conductive reflecting film 68 places reflection can not produce factitious sensation yet.
In addition, similar with the situation that is formed with through hole 70 in the conductive reflecting film 68, in this illustrative embodiments, the distance between centers L of adjacent through hole 92 is set in 10 μ m because the internal diameter size D of through hole 92 is set at 5 μ m, so their ratio becomes 0.5.As a result, can guarantee to have 80% reflectivity when not forming through hole 92.In this way, be set at 0.5 by the ratio with the internal diameter size D of through hole 92 and the distance between centers L of adjacent through hole 92, although formed through hole 92 these facts, light can be reflected fully at electrochromic film 86 places.
In addition, in this illustrative embodiments, although the distance between centers L of adjacent through hole 92 is set in 10 μ m, it forms position irregular (at random), and is similar to through hole 70.Therefore, the rule that does not produce the light of electrochromic film 86 places reflection is interfered.As a result, can make reflection image more clear.
It should be noted that, the formation of the EC mirror 80 of this illustrative embodiments is substantially the same with the formation of the EC mirror 60 of the 4th illustrative embodiments, and difference is to be provided with the electrochromic film 86 that wherein is formed with through hole 92 and replaces conductive reflecting film 68 these facts.Therefore, EC mirror 80 has realized the effect identical with EC mirror 60 basically, and can obtain the effect identical with EC mirror 60.
It should be noted that this 5th illustrative embodiments is the variation of first to the 3rd illustrative embodiments.Used and be provided with carbon film 30 and describe as the EC mirror 80 of reduction reaction compensating unit.
But, illustrated being provided with in the EC mirror 210 of anionic reactive film 230 as the reduction reaction compensating unit can be provided with the electrochromic film 86 that wherein is formed with through hole 92 and replace anionic reactive film 230 in second illustrative embodiments.So EC mirror 80 has realized the effect identical with EC mirror 210 basically, and can obtain the effect identical with EC mirror 210.
In addition, in the 3rd illustrative embodiments, in the illustrated EC mirror 310 that is provided with conducting film 28 that forms by silver and the difficulty soluble salt film 330 that constitutes the reduction reaction compensating unit, the electrochromic film 86 that wherein is formed with through hole 92 can be set replace conducting film.So EC mirror 80 has realized the effect identical with EC mirror 310 basically, and can obtain the effect identical with EC mirror 310.
The formation of＜the six illustrative embodiments 〉
Next step will describe the 6th illustrative embodiments of the present invention.
In Figure 11, the formation of the EC mirror 110 of this illustrative embodiments is shown in diagrammatic cross-section.
As shown in this figure, EC mirror 110 is not provided with conductive reflecting film 68, the substitute is, and is provided with conductive reflecting film 118.Conductive reflecting film 118 is made of first conductive reflecting film 120 and second conductive reflecting film 122 that plays the effect of electric conductivity diaphragm.The side opposite that first conductive reflecting film 120 is formed on electrochromic film 16 with base main body 14.First conductive reflecting film 120 is formed by aluminium (Al), silver (Ag) or indium (In) etc.Otherwise second conductive reflecting film 122 forms by compare more corrosion resistant metal (for example, rhodium (Rh), ruthenium (Ru), palladium (Pd), nickel (Ni) or chromium (Cr) etc.) with first conductive reflecting film 120.
In addition, the peripheral edge portion of second conductive reflecting film 122 is formed than the peripheral edge portion position of first conductive reflecting film 120 more toward the outer side.As a result, whole first conductive reflecting film 120 is covered by second conductive reflecting film 122 from a side opposite with electrochromic film 16.
In addition, although in the 4th and the 5th illustrative embodiments, through hole 70 is formed in the conductive reflecting film 68, but as shown in figure 12, in this illustrative embodiments, according to the condition identical with through hole 70, in first conductive reflecting film 120, be formed with the through hole 124 suitable with through hole 70, in second conductive reflecting film 122, be formed with the through hole 126 suitable with through hole 70.
The effect of＜the six illustrative embodiments and effect 〉
In the EC mirror 110 of above-mentioned formation,, and be reflected at first conductive reflecting film, 120 places from the light transmission base main body 14 and the electrochromic film 86 of the side incident opposite of base main body 14 with electrochromic film 16.And, if being reflected at first conductive reflecting film, 120 places, any light do not see through first conductive reflecting film 120, it is reflected at second conductive reflecting film, 122 places so.
Simultaneously, electrolytic solution 34 side opposite that be encapsulated in conductive reflecting film 118 with electrochromic film 86.In this EC mirror 110, electrolytic solution 34 sides of main catoptrical first conductive reflecting film 120 are covered by second conductive reflecting film 122, and described second conductive reflecting film 122 forms by comparing more corrosion resistant metal with first conductive reflecting film 120.Therefore, protected by second conductive reflecting film 122 with respect to electrolytic solution 34, the first conductive reflecting films 120, first conductive reflecting film 120 becomes and more is difficult to be corroded.As a result, first conductive reflecting film 120 can be chronically with the mode reflected light of excellence.
In addition, the peripheral edge portion of second conductive reflecting film 122 than the peripheral edge portion position of first conductive reflecting film 120 more toward the outer side.So; whole first conductive reflecting film 120 is covered by second conductive reflecting film 122 from a side opposite with electrochromic film 16; with respect to electrolytic solution 34; the surface at a side place opposite not only with electrochromic film 16; and the peripheral end of first conductive reflecting film 120; all protected, thereby can suppress or prevent the corrosion of first conductive reflecting film 120 effectively by second conductive reflecting film 122.
And, because the light that second conductive reflecting film 122 reflects from base main body 14 sides itself, so although the light of the peripheral edge portion of tranmittance first conductive reflecting film 120 base main body 14 more toward the outer side is not reflected at first conductive reflecting film, 120 places, but the substitute is, it is reflected by second conductive reflecting film 122.The result, (in other words the reflection of light zone can access widens, because formation is set to whole first conductive reflecting film 120 and is covered by second conductive reflecting film 122, so even make first conductive reflecting film 120 littler, the reflection of light zone does not narrow yet).
It should be noted that, the formation of the EC mirror 110 of this illustrative embodiments is substantially the same with the formation of the EC mirror 60 of the 4th illustrative embodiments, and difference is to be provided with conductive reflecting film 68 these facts that the conductive reflecting film 118 that comprises first conductive reflecting film 120 that is formed with through hole 124 and be formed with second conductive reflecting film 122 of through hole 126 replaces being formed with through hole 70.Therefore, EC mirror 110 has realized the effect identical with EC mirror 60 basically, and can obtain the effect identical with EC mirror 60.
In addition, although the EC mirror of this illustrative embodiments 110 has the formation that wherein is provided with electrochromic film 16, but being provided with in the situation of formation that electrochromic film 86 replaces electrochromic film 16 as shown in figure 13, except that the effect and effect of this illustrative embodiments, also realized the effect identical, and can obtain the effect identical with EC mirror 80 with the EC mirror 80 of the 5th illustrative embodiments.
It should be noted that this 6th illustrative embodiments is the variation of first to the 3rd illustrative embodiments.Used and be provided with carbon film 30 and describe as the EC mirror 110 of reduction reaction compensating unit.
But, illustrated being provided with in the EC mirror 210 of anionic reactive film 230 as the reduction reaction compensating unit in second illustrative embodiments can be provided with first conductive reflecting film 120 that is formed with through hole 124 and replace anionic reactive film 230 with second conductive reflecting film 122 that is formed with through hole 126.So EC mirror 110 has realized the effect identical with EC mirror 210 basically, and can obtain the effect identical with EC mirror 210.And, in EC mirror 210, electrochromic film 86 can be set replace electrochromic film 16.So, realized the effect identical with the EC mirror 80 of the 5th illustrative embodiments, can also obtain the effect identical with EC mirror 80.
In addition, in the 3rd illustrative embodiments in the illustrated EC mirror 310 that is provided with conducting film 28 that is formed by silver and the difficulty soluble salt film 330 that constitutes the reduction reaction compensating unit, second conductive reflecting film 122 that first conductive reflecting film 120 that is formed with through hole 124 can be set and be formed with through hole 126 replaces conducting film 28.So EC mirror 310 has realized the effect identical with EC mirror 10 basically, and can obtain the effect identical with EC mirror 310.And, electrochromic film 86 can be set replace electrochromic film 16.So, realized the effect identical with the EC mirror 80 of the 5th illustrative embodiments, can also obtain the effect identical with EC mirror 80.
The formation of＜the seven illustrative embodiments 〉
Next step will describe the 7th illustrative embodiments of the present invention.
In Figure 14, the formation of EC mirror 140 of the present invention is shown in diagrammatic cross-section.
As shown in this figure, in EC mirror 140, between base main body 14 and electrochromic film 16, be provided with ELD 142.ELD 142 is by tin indium oxide (In 2O 3: Sn, perhaps so-called " ITO "), tin oxide (SnO 2), fluorine-doped tin oxide (SnO 2: F) or zinc paste (ZnO 2) wait formation, perhaps the potpourri by these materials forms.ELD 142 is connected to the negative pole of direct supply 44.
And the surface in the side opposite with ELD 142 of electrochromic film 16 does not form conductive reflecting film 18, conductive reflecting film 68 or conductive reflecting film 118, the substitute is, and is formed with transparent lithium ion and sees through film 144.Lithium ion sees through film 144 and is formed by lithium fluoride or magnesium fluoride, when switch 42 switches to the ON state, and the lithium ion (Li in the electrolytic solution 34 +) see through thus.In addition, the surface of a side opposite with electrochromic film 16 that sees through film at lithium ion is formed with by silver or contains the optical reflection film 146 that silver alloy constitutes.
The effect of＜the seven illustrative embodiments and effect 〉
In the EC mirror 140 of above-mentioned formation, when the OFF of switch 42 state, it is substantial transparent that ELD 142 and lithium ion see through film 144, the result, see through film 144 from light transmission base main body 14, ELD 142, electrochromic film 16 and the lithium ion of the side incident opposite of base main body 14, and be reflected at optical reflection film 146 places with electrochromic film 16.In addition, the light transmission lithium ion that is reflected at optical reflection film 146 places sees through film 144, electrochromic film 16, ELD 142 and base main body 14.
On the other hand, when switch 42 switches to the ON state, moved through the electronics (e in loop 40 -) enter in the electrochromic film 16, constitute the electrolytical lithium ion (Li of electrolytic solution 34 +) see through film 144 through optical reflection film 146 and lithium ion, and enter in the electrochromic film 16.As a result, with the similar mode of first illustrative embodiments, electrochromic film 16 is colored blue, reduces thereby compare reflectivity before being colored with electrochromic film 16.
In this illustrative embodiments, optical reflection film 146 is by silver or contain silver alloy and form.If by silver or contain the optical reflection film 146 that silver alloy forms and be formed directly into, exist the silver of optical reflection film 146 can be diffused into the tungstic acid of electrochromic film 16 and the possibility that tungstic acid is understood flavescence by on the formed electrochromic film 16 of tungstic acid.
But, in this illustrative embodiments, because seeing through film 144, lithium ion is arranged between electrochromic film 16 and the optical reflection film 146, so prevent from or suppressed silver effectively to be diffused into electrochromic film 16.As a result, even optical reflection film 146 by silver or contain silver alloy and form, also can prevent or suppress effectively the flavescence of electrochromic film 16, and can keep quality for a long time excellently.
It should be noted that, because the formation of this illustrative embodiments is substantially the same with the formation of first illustrative embodiments, difference is to be provided with ELD 142 these facts and is provided with transparent lithium ion and replaces conductive reflecting film 18 these facts through film 144 and optical reflection film 146 between base main body 14 and electrochromic film 16, so this illustrative embodiments has realized the effect identical with first illustrative embodiments basically, and can obtain identical effect.
It should be noted that this 7th illustrative embodiments is the variation of first to the 3rd illustrative embodiments.Used and be provided with carbon film 30 and describe as the EC mirror 140 of reduction reaction compensating unit.
But, illustrated being provided with in the EC mirror 210 of anionic reactive film 230 as the reduction reaction compensating unit in second illustrative embodiments, can between base main body 14 and electrochromic film 16, ELD 142 be set, and can be provided with that transparent lithium ion sees through film 144 and optical reflection film 146 replaces conductive reflecting film 18.So EC mirror 140 has realized the effect identical with EC mirror 210 basically, and can obtain the effect identical with EC mirror 210.
In addition, in the 3rd illustrative embodiments in the illustrated EC mirror 310 that is provided with conducting film 28 that forms by silver and the difficulty soluble salt film 330 that constitutes the reduction reaction compensating unit, can between base main body 14 and electrochromic film 16, ELD 142 be set, and can be provided with that transparent lithium ion sees through film 144 and optical reflection film 146 replaces conductive reflecting film 18.So EC mirror 140 has realized the effect identical with EC mirror 310 basically, and can obtain the effect identical with EC mirror 310.
The formation of＜the eight illustrative embodiments 〉
Next step will describe the 8th illustrative embodiments of the present invention.
In Figure 15, the formation of the EC mirror 160 of this illustrative embodiments is shown in diagrammatic cross-section.
As shown in this figure, the formation of EC mirror 160 is substantially the same with the formation of the EC mirror 140 of the 7th illustrative embodiments, but EC mirror 160 is not provided with optical reflection film 146, the substitute is, and is provided with optical reflection film 166.Constitute although optical reflection film 166 is both by silver or contains silver alloy with optical reflection film 146, its neighboring contacts with the neighboring of ELD 142 and conducts electricity with it.
The effect of＜the eight illustrative embodiments and effect 〉
In the EC mirror 160 of above-mentioned formation, owing to contact with the neighboring of ELD 142 and conduct electricity with it by silver or the neighboring that contains the optical reflection film 166 that silver alloy forms, when switch 42 switches to the ON state, can make optical reflection film 166 play electrode.
It should be noted that, because the formation of this illustrative embodiments is substantially the same with the formation of the 7th illustrative embodiments, difference is to be provided with optical reflection film 166 and replaces optical reflection film 146 these facts, so this illustrative embodiments has realized the effect identical with the 7th illustrative embodiments, and can obtain identical effect.
It should be noted that this 8th illustrative embodiments is the variation of first to the 3rd illustrative embodiments.Used and be provided with carbon film 30 and describe as the EC mirror 160 of reduction reaction compensating unit.
But, illustrated being provided with in the EC mirror 210 of anionic reactive film 230 as the reduction reaction compensating unit in second illustrative embodiments, can between base main body 14 and electrochromic film 16, ELD 142 be set, and can be provided with that transparent lithium ion sees through film 144 and optical reflection film 166 replaces conductive reflecting film 18.So EC mirror 160 has realized the effect identical with EC mirror 210 basically, and can obtain the effect identical with EC mirror 210.
In addition, in the 3rd illustrative embodiments in the illustrated EC mirror 310 that is provided with conducting film 28 that forms by silver and the difficulty soluble salt film 330 that constitutes the reduction reaction compensating unit, can between base main body 14 and electrochromic film 16, ELD 142 be set, and can be provided with that transparent lithium ion sees through film 144 and optical reflection film 166 replaces conductive reflecting film 18.So EC mirror 160 has realized the effect identical with EC mirror 310 basically, and can obtain the effect identical with EC mirror 310.
The formation of＜the nine illustrative embodiments 〉
In the disclosed EC mirror of instructions of 3,844, No. 636 patents of the U.S., palladium is used as optical reflection film.
Simultaneously, owing to use the reflectivity of optical reflection film of palladium lower, so the preferred aluminium with high reflectance etc. of using is as optical reflection film.But, because electrolytic solution is encapsulated between the counter electrode film (opposing electrode film) and optical reflection film of a side opposite with electrochromic film of being located at optical reflection film, so when aluminium etc. is used for optical reflection film, in optical reflection film, take place such as deteriorations such as corrosion easily.
What therefore, need is the EC mirror that is difficult to take place the deterioration of optical reflection film.
In Figure 16, the formation of the EC mirror 1010 of the 9th illustrative embodiments of the present invention is shown in diagrammatic cross-section.
As shown in this figure, in EC mirror 1010, conductive reflecting film 1018 is made of first conductive reflecting film 1020 and second conductive reflecting film 1022 that plays the effect of electric conductivity diaphragm.
And second conductive reflecting film 1022 is formed its peripheral edge portion than the peripheral edge portion position of first conductive reflecting film 1020 more toward the outer side.As a result, whole first conductive reflecting film 1020 is covered by second conductive reflecting film 1022 from a side opposite with electrochromic film 16.
The side opposite that first conductive reflecting film 1020 is formed on electrochromic film 16 with base main body 14.First conductive reflecting film 1020 is formed by aluminium (Al), silver (Ag) or indium (In) etc.Otherwise second conductive reflecting film 1022 forms by compare more corrosion resistant metal (for example, rhodium (Rh), ruthenium (Ru), palladium (Pd), nickel (Ni) or chromium (Cr) etc.) with first conductive reflecting film 1020.
As shown in figure 17, in first conductive reflecting film 1020, be formed with a plurality of fine through hole 1048 that connects first conductive reflecting film 1020 at its thickness direction, in second conductive reflecting film 1022, be formed with a plurality of fine through hole 1050 that connects second conductive reflecting film 1022 at its thickness direction.Through hole 1048 communicates with each other with through hole 1050.And through hole 1048 and 1050 internal diameter (diameter of interior perimembranous) dimension D are below the 20 μ m, especially, in this illustrative embodiments, are 5 μ m.In addition, through hole 1048 and 1050 irregular basically (at random) forms in conductive reflecting film 1018.But, to be configured to make the distance between centers L of adjacent through hole 1048 and 1050 be 10 μ m to through hole 1048 and 1050.
Through hole 1048 and 1050 forms by following manner: photomask (printing the pattern of through hole 1048 and 1050 on the conductive reflecting film 1018 that is coated with photoresist) is set, expose, remove then and through hole 1048 and 1050 corresponding photoresists, and dissolve conductive reflecting film 1018 with etching liquid.
In addition, in the surface of face side substrate 12 sides of conducting film 28, be formed with have electric conductivity carbon film 30 as the reduction reaction compensating unit.
The effect of＜the nine illustrative embodiments and effect 〉
In the EC mirror 1010 of above-mentioned formation, when the OFF of switch 42 state, electrochromic film 16 substantial transparent that becomes, therefore, from the light transmission base main body 14 and the electrochromic film 16 of the side incident opposite of base main body 14, and be reflected at first conductive reflecting film, 1020 places with electrochromic film 16.And, if being reflected at first conductive reflecting film, 1020 places, any light do not see through first conductive reflecting film 1020, it is reflected at second conductive reflecting film, 1022 places so.
In addition, light transmission electrochromic film 16 and the base main body 14 that is reflected at first conductive reflecting film 1020 or second conductive reflecting film, 1022 places.The result is in this illustrative embodiments of above-mentioned formation, and light reflectivity becomes about 55%.
As mentioned above, in this EC mirror 1010, in first conductive reflecting film 1020, be formed with through hole 1048, in second conductive reflecting film 1022, be formed with through hole 1050.Therefore, when switch 42 switches to the ON state and applies voltage, owing to constitute the electrolytical lithium ion (Li of electrolytic solution 34 +) pass through hole 1048 and 1050 these facts, so, and do not forming the location lithium ion (Li of through hole 1048 and 1050 +) compare when seeing through conductive reflecting film 1018, they enter in the electrochromic film 16 quickly.As a result, reduction reaction takes place more quickly in electrochromic film 16, whole electrochromic film 16 is by more promptly painted.
In addition, in this illustrative embodiments, because internal diameter (diameter of the interior perimembranous) dimension D of through hole 1048 and 1050 is set at 5 μ m (promptly 20 μ m are following), so through hole 1048 and 1050 can not directly be observed visually basically.So even form through hole 1048 and at 1050 o'clock, the light time of visual inspection EC mirror 1010 places reflection can not produce factitious sensation yet.
Simultaneously, in Fig. 8, shown internal diameter (diameter of the interior perimembranous) dimension D of through hole 1048 and 1050 and adjacent through hole 1048 and 1050 distance between centers L ratio and owing to form relation between the minimizing ratio of reflectivity of the EC mirror 1010 due to the through hole 1048 and 1050.In this illustrative embodiments, the distance between centers L of adjacent through hole 1048 and 1050 is set in 10 μ m because the internal diameter size D of through hole 1048 and 1050 is set in 5 μ m, so their ratio becomes 0.5.As a result, as shown in Figure 8, can guarantee to have do not forming 80% reflectivity of through hole 1048 and at 1050 o'clock.In this way, be set at 0.5 by ratio with the internal diameter size D of through hole 1048 and 1050 and the distance between centers L of adjacent through hole 1048 and 1050, although the through hole 1048 of formation and 1050 these facts are arranged, light can be reflected fully at conductive reflecting film 1018 places.
In addition, in this illustrative embodiments, although the distance between centers L of adjacent through hole 1048 and 1050 is set in 10 μ m, it forms position irregular (at random).Therefore, the rule that does not produce the light of conductive reflecting film 1018 places reflection is interfered.As a result, can make reflection image more clear.
In addition, in this EC mirror 1010, the side opposite that electrolytic solution 34 is encapsulated in conductive reflecting film 1018 with electrochromic film 16.In this EC mirror 1010, mainly electrolytic solution 34 sides of first conductive reflecting film 1020 that light is reflected are covered by second conductive reflecting film 1022, and second conductive reflecting film 1022 forms by comparing more corrosion resistant metal with first conductive reflecting film 1020.Therefore, protected by second conductive reflecting film 1022 with respect to electrolytic solution 34, the first conductive reflecting films 1020, first conductive reflecting film 1020 becomes and more is difficult to be corroded.As a result, first conductive reflecting film 1020 can be chronically with the mode reflected light of excellence.
In addition, the peripheral edge portion of second conductive reflecting film 1022 than the peripheral edge portion position of first conductive reflecting film 1020 more toward the outer side.So; whole first conductive reflecting film 1020 is covered by second conductive reflecting film 1022 from a side opposite with electrochromic film 16; with respect to electrolytic solution 34; the surface at a side place opposite not only with electrochromic film 16; and the peripheral end of first conductive reflecting film 1020; all protected, thereby can suppress or prevent the corrosion of first conductive reflecting film 1020 effectively by second conductive reflecting film 1022.
And, because the light that second conductive reflecting film 1022 reflects from base main body 14 sides itself, so although the light of the peripheral edge portion of tranmittance first conductive reflecting film 1020 base main body 14 more toward the outer side is not reflected at first conductive reflecting film, 1020 places, but the substitute is, it is reflected by second conductive reflecting film 1022.The result, (in other words the reflection of light zone can access widens, because formation is set to whole first conductive reflecting film 1020 and is covered by second conductive reflecting film 1022, so even make first conductive reflecting film 120 littler, the reflection of light zone does not narrow yet).
When the mirror main body of the inside rear-view mirror that is used for vehicle for example such as above-mentioned EC mirror 1010 or outside rear-view mirror (peephole or fender mirror) etc., in the daytime the time, thereby switch 42 can be remained on the OFF state and carry out backsight with high reflectance, when situations such as night, when the vehicle at rear is opened headlight, make electrochromic film 16 painted and reduction reflectivity by switch 42 being switched to the ON state, can reduce the reflected light of headlight, and reduce dazzle.
It should be noted that the EC mirror 1010 of this illustrative embodiments is corresponding to following formation: the conductive reflecting film 1018 that is made of first conductive reflecting film 1020 and second conductive reflecting film 1022 is set at carbon film 30 in as the EC mirror 10 of first illustrative embodiments of reduction reaction compensating unit and replaces conductive reflecting film 18.Therefore, EC mirror 1010 has realized the effect identical with EC mirror 10 basically, and can obtain the effect identical with EC mirror 10.
The formation of＜the ten illustrative embodiments 〉
In Figure 18, the formation of the EC mirror 1060 of the tenth illustrative embodiments of the present invention is shown in diagrammatic cross-section.
As shown in this figure, EC mirror 1060 is not provided with electrochromic film 16, the substitute is, and is provided with electrochromic film 1066.Electrochromic film 1066 is by forming with electrochromic film 16 identical materials, and form the thickness identical with electrochromic film 16, but, as shown in figure 19, in electrochromic film 1066, be formed with a plurality of fine through hole 1068 that connects at its thickness direction.Through hole 1068 communicates with through hole 1048 and 1050, and its internal diameter (diameter of interior perimembranous) dimension D is below the 20 μ m, especially, is set in 5 μ m in this illustrative embodiments.In addition, through hole 1068 irregular basically (at random) forms in electrochromic film 1066.But, the distance between centers L of adjacent through hole 1068 is set in 10 μ m.
Through hole 1068 forms by following manner: photomask (pattern of printing through hole 1068 on the electrochromic film 1066 that is coated with photoresist) is set, expose, remove then and through hole 1068 corresponding photoresists, and dissolve electrochromic film 1066 with etching liquid.
The effect of＜the ten illustrative embodiments and effect 〉
In the EC mirror 1060 of above-mentioned formation, in conductive reflecting film 1018, be formed with through hole 1048 and 1050, in electrochromic film 1066, be formed with through hole 1068.So, when switch 42 switches to the ON state and applies voltage, at first, owing to constitute the electrolytical lithium ion (Li of electrolytic solution 34 +) pass through hole 1048 and 1050 these facts, so, and do not forming the location lithium ion (Li of through hole 1048 and 1050 +) compare when seeing through conductive reflecting film 1018, they arrive electrochromic film 1066 quickly.
And the lithium ion that has arrived electrochromic film 1066 enters through hole 1068 and enters the electrochromic film 1066 from the interior perimembranous of through hole 1068.As a result, quicker generation reduction reaction in electrochromic film 1066, whole electrochromic film 1066 is by more promptly painted.
In addition, in this illustrative embodiments, because internal diameter (diameter of the interior perimembranous) dimension D of through hole 1068 is set at 5 μ m (promptly 20 μ m are following), so through hole 1068 can not directly be observed visually basically.So even when forming through hole 1068, the light time of visual inspection conductive reflecting film 1018 places reflection can not produce factitious sensation yet.
In addition, similar with the situation that is formed with through hole 1048 and 1050 in the conductive reflecting film 1018, in this illustrative embodiments, the distance between centers L of adjacent through hole 1068 is set in 10 μ m because the internal diameter size D of through hole 1068 is set at 5 μ m, so their ratio becomes 0.5.As a result, can guarantee to have 80% reflectivity when not forming through hole 1068.In this way, be set at 0.5 by the ratio with the internal diameter size D of through hole 1068 and the distance between centers L of adjacent through hole 1068, although formed through hole 1068 these facts, light can be reflected fully at electrochromic film 1066 places.
In addition, in this illustrative embodiments, although the distance between centers L of adjacent through hole 1068 is set in 10 μ m, it forms position irregular (at random), and is similar with 1050 to through hole 1048.Therefore, the rule that does not produce the light of electrochromic film 1066 places reflection is interfered.As a result, can make reflection image more clear.
It should be noted that, the formation of the EC mirror 1060 of this illustrative embodiments is substantially the same with the formation of the EC mirror 1010 of the 9th illustrative embodiments, and difference is to be provided with the electrochromic film 1066 that wherein is formed with through hole 1068 and replaces this fact of conductive reflecting film.Therefore, EC mirror 1060 has realized the effect identical with EC mirror 1010 basically, and can obtain the effect identical with EC mirror 1010.
The formation of＜the ten one illustrative embodiments 〉
Next step will describe the 11 illustrative embodiments of the present invention.
In Figure 20, the formation of the EC mirror 1210 of this illustrative embodiments is shown in diagrammatic cross-section.
As shown in this figure, EC mirror 1210 is not provided with carbon film 30, the substitute is, and is provided with anionic reactive film 1212 as the reduction reaction compensating unit.
The effect and the effect of＜the ten one illustrative embodiments 〉
It should be noted that the EC mirror 1210 of this illustrative embodiments is equivalent to following formation: the conductive reflecting film 1018 that is made of first conductive reflecting film 1020 and second conductive reflecting film 1022 is set at anionic reactive film 230 in as the EC mirror 210 of second illustrative embodiments of reduction reaction compensating unit and replaces conductive reflecting film 18.Therefore, EC mirror 1210 has realized the effect identical with EC mirror 210 basically, and can obtain the effect identical with EC mirror 210.
In other words, as described in above second illustrative embodiments, in this illustrative embodiments, enough reduction reactions are taken place, so, as mentioned above, by switch 42 being switched to the ON state and applying voltage, electrochromic film 16 can obtain painted fully.
In addition, in this illustrative embodiments, when making electrochromic film 16 painted, the voltage that is applied can be low to moderate 1.3V.So, when switch 42 switched to OFF state and conductive reflecting film 1018 and conducting film 28 short circuits, the backward reaction of following formula 5a or formula 5b took place, electrochromic film 16 decolours rapidly.
When the mirror main body of the inside rear-view mirror that is used for vehicle for example such as above-mentioned EC mirror 1210 or outside rear-view mirror (peephole or fender mirror) etc., in the daytime the time, thereby switch 42 can be remained on the OFF state and carry out backsight with high reflectance, when situations such as night, when the vehicle at rear is opened headlight, make electrochromic film 16 painted and reduction reflectivity by switch 42 being switched to the ON state, can reduce the reflected light of headlight, and reduce dazzle.
The formation of＜the ten two illustrative embodiments 〉
In Figure 21, the formation of the EC mirror 1220 of the 12 illustrative embodiments of the present invention is shown in diagrammatic cross-section.
As shown in the drawing, in EC mirror 1220, conducting film 28 is formed by silver (Ag).Surface in face side substrate 12 sides of conducting film 28 does not form carbon film 30, the substitute is, be formed with constitute the reduction reaction compensating unit difficulty soluble salt film 1224 as separating out film.Difficulty soluble salt film 1224 is formed by silver chloride, bromine chloride or sulfur chloride cyanate etc., and especially, in this illustrative embodiments, difficulty soluble salt film 1224 is formed by silver chloride.
The effect and the effect of＜the ten two illustrative embodiments 〉
It should be noted that, the EC mirror 1220 of this illustrative embodiments is equivalent to following formation: in conducting film 28 that disposes argentiferous and the EC mirror 310 as the 3rd illustrative embodiments of the difficulty soluble salt film 330 of reduction reaction compensating unit, the conductive reflecting film 1018 that is made of first conductive reflecting film 1020 and second conductive reflecting film 1022 is set replaces conductive reflecting film 18.Therefore, EC mirror 1220 has realized the effect identical with EC mirror 310 basically, and can obtain the effect identical with EC mirror 310.
In other words, as described in above the 3rd illustrative embodiments, in this illustrative embodiments, owing in electrochromic film 16, compensatory reaction takes place reliably with respect to reduction reaction, so when making electrochromic film 16 painted, the voltage that is applied can be low to moderate 1.3V.So, when switch 42 switched to OFF state and conductive reflecting film 1018 and conducting film 28 short circuits, the backward reaction of following formula 1 and formula 8 took place, electrochromic film 16 decolours rapidly.
When the mirror main body of the inside rear-view mirror that is used for vehicle for example such as above-mentioned EC mirror 1220 or outside rear-view mirror (peephole or fender mirror) etc., in the daytime the time, thereby switch 42 can be remained on the OFF state and carry out backsight with high reflectance, when situations such as night, when the vehicle at rear is opened headlight, make electrochromic film 16 painted and reduction reflectivity by switch 42 being switched to the ON state, can reduce the reflected light of headlight, and reduce dazzle.
The formation of＜the ten three illustrative embodiments 〉
In Figure 22, the formation of the EC mirror 1240 of the 13 illustrative embodiments of the present invention is shown in diagrammatic cross-section.
As shown in this figure, in EC mirror 1240, do not form carbon film 30 in the surface of face side substrate 12 sides of conducting film 28.In addition, electrolytic solution 1244 is encapsulated in replacement electrolytic solution 34 between face side substrate 12 and the rear side substrate 24.
Except that the material that constitutes electrolytic solution 34, electrolytic solution 1244 also contains ferrocene (Fe (C 5H 5) 2), it is the neutral material as the oxygenant that constitutes the reduction reaction compensating unit.
The effect and the effect of＜the ten three illustrative embodiments 〉
In this EC mirror 1240, in when, because switch 42 switches to the ON state reduction reaction of above-mentioned formula 1 taking place in electrochromic film 16 when, shown in 9, the ferrocene that contains in the electrolytic solution 1244 lotus that becomes positively charged.As a result, carried out and above-mentioned reduction reaction corresponding compensation.
Fe (C 5H 5) 2→ [Fe (C 5H 5) 2] +(formula 9)
In this way, in this illustrative embodiments, owing in electrochromic film 16, compensatory reaction takes place reliably, so when making electrochromic film 16 painted, the voltage that is applied can be low to moderate 1.3V with respect to reduction reaction.So, when switch 42 switched to OFF state and conductive reflecting film 1018 and conducting film 28 short circuits, the backward reaction of following formula 1 and formula 9 took place, electrochromic film 16 decolours rapidly.
When the mirror main body of the inside rear-view mirror that is used for vehicle for example such as above-mentioned EC mirror 1240 or outside rear-view mirror (peephole or fender mirror) etc., in the daytime the time, thereby switch 42 can be remained on the OFF state and carry out backsight with high reflectance, when situations such as night, when the vehicle at rear is opened headlight, make electrochromic film 16 painted and reduction reflectivity by switch 42 being switched to the ON state, can reduce the reflected light of headlight, and reduce dazzle.
It should be noted that, although above-mentioned the 11 illustrative embodiments to the 13 illustrative embodiments are the variation of the 9th illustrative embodiments, the 11 illustrative embodiments to the 13 illustrative embodiments can be configured to the variation of the tenth illustrative embodiments.
Above embodiments of the present invention are illustrated, but it will be apparent for a person skilled in the art that the present invention is not limited to these embodiments.
According to first scheme of the present invention, a kind of EC mirror is provided, described EC mirror comprises: electrochromic film, described electrochromic film is colored owing to carrying out reduction reaction; Conductive reflecting film with electric conductivity, described conductive reflecting film are formed on the side of thickness direction of described electrochromic film and the light that reflection has seen through described electrochromic film; Conducting film with electric conductivity, described conducting film are arranged on the side of thickness direction of described electrochromic film and a side opposite with described electrochromic film of described conductive reflecting film; Electrolytic solution, described electrolytic solution comprises lithium ion, and be encapsulated between described conductive reflecting film and the described conducting film, wherein, since apply voltage make described conducting film for just and described conductive reflecting film for bearing, so described lithium ion is towards described electrochromic film side shifting, and supply to the reduction reaction of described electrochromic film; With the reduction reaction compensating unit, described reduction reaction compensating unit by storage be in the electric charge that applies described voltage status or by with described electrolytic solution in negative ion carry out oxidation reaction, compensate described reduction reaction.
In the EC mirror of above-mentioned first scheme, the light that sees through electrochromic film is reflected by conductive reflecting film.
When apply voltage make conducting film for just and conductive reflecting film when negative, the lithium ion that is encapsulated in the electrolytic solution between conducting film and the conductive reflecting film is towards the electrochromic film side shifting.Because lithium ion is towards the electrochromic film side shifting, so electrochromic film carries out reduction reaction, electrochromic film is owing to this reduction reaction is colored.Because electrochromic film is colored in this way, so the transmitance of the light in the electrochromic film reduces.
In above-mentioned first scheme, formation can be set to, and the reduction reaction compensating unit can comprise the carbon film with electric conductivity, and described carbon film is formed on the conductive reflecting film side of described conducting film and contains activated charcoal.
According to above-mentioned formation, when apply voltage make conducting film for just and conductive reflecting film when negative, the negative ion of electrolytic solution moves towards a side (promptly towards the carbon film side) opposite with electrochromic film, and negative ion is stored in the carbon film.Carbon film is formed and contains activated charcoal.Because activated charcoal porous thereby have high surface area is so it can store many negative ion.So,, reduction reaction is taken place fully even the above-mentioned voltage that is applied to conducting film and conductive reflecting film is lower.And, owing in this way even with low voltage reduction reaction is taken place, after applying the voltage end, electrochromic film is easily decoloured.
In first scheme, formation can be set to, and in described conductive reflecting film, is formed with a plurality of fine through hole that connects described conductive reflecting film at the thickness direction of described conductive reflecting film.
According to above-mentioned formation, when apply voltage make conducting film for just and conductive reflecting film when negative, the negative ion of electrolytic solution is towards the anionic reactive film side shifting that is formed by electric conductive polymer or redox polymers, the anionic reactive film is by the negative ion oxidation.
In this way, because the anionic reactive film is formed by electric conductive polymer or redox polymers, many negative ion are fed in the oxidation of anionic reactive film, thereby, even the above-mentioned voltage that is applied to conducting film and conductive reflecting film is lower, reduction reaction is taken place fully.And, owing in this way even with low voltage reduction reaction is taken place, after applying the voltage end, electrochromic film is easily decoloured.
In first scheme, formation can be set to, and in described electrochromic film, is formed with along the thickness direction of the described electrochromic film a plurality of fine hole portion at described conductive reflecting film side opening.
According to above-mentioned formation, when apply voltage make conducting film for just and conductive reflecting film when negative, the lithium ion that is encapsulated in the electrolytic solution between conducting film and the conductive reflecting film is towards the electrochromic film side shifting.Because lithium ion is towards the electrochromic film side shifting, so electrochromic film carries out reduction reaction, electrochromic film is owing to this reduction reaction is colored.Because electrochromic film is colored in this way, so the transmitance of the light in the electrochromic film reduces.
When applying voltage as mentioned above, the negative ion that constitutes the difficulty soluble salt of electrolytic solution moves to the conducting film side.The ionic reaction of the negative ion of these difficulty soluble salts and the silver that constitutes conducting film is separated out separating out on the film at the difficulty soluble salt of the conductive reflecting film side that is arranged on conducting film.
In this way, since conducting film and separate out the film place can make with electrochromic film in the corresponding oxidation reaction of reduction reaction take place fully, so, even the above-mentioned voltage that is applied to conducting film and conductive reflecting film is lower, reduction reaction is taken place fully.And, owing in this way even with low voltage reduction reaction is taken place, after applying the voltage end, electrochromic film is easily decoloured.
In above-mentioned first scheme, formation can be set to, described conductive reflecting film comprises: have first conductive reflecting film of electric conductivity, described first conductive reflecting film is formed on a side of the thickness direction of described electrochromic film, and reflection has seen through the light of described electrochromic film; With the electric conductivity diaphragm with electric conductivity, described electric conductivity diaphragm is formed on a side opposite with described electrochromic film of described first conductive reflecting film, and corrosion-resistant material forms by comparing more with the material that constitutes described first conductive reflecting film.
According to above-mentioned formation; electrolytic solution constitutes that also contain can be by the reaction material of neutral molecule or the oxidation of negative ion institute except that lithium ion; when apply voltage make conducting film for just and first conductive reflecting film and electric conductivity diaphragm when negative, oxidation reaction takes place in the reaction material that constitutes electrolytic solution.So the reduction reaction in the above-mentioned electrochromic film is compensated, even and the above-mentioned voltage that is applied to conducting film and first conductive reflecting film and electric conductivity diaphragm lower, reduction reaction is taken place fully.
And, owing in this way even with low voltage the reduction reaction in the electrochromic film is taken place, after applying the voltage end, electrochromic film is easily decoloured.
In above-mentioned first scheme, formation can be set to, and described electric conductivity diaphragm comprises second conductive reflecting film with electric conductivity, and described second conductive reflecting film reflection is from the light of the described first conductive reflecting film side.
According to above-mentioned formation, in conductive reflecting film, be formed with a plurality of fine through hole that connects conductive reflecting film at the thickness direction of conductive reflecting film.Therefore, when apply voltage make conducting film for just and conductive reflecting film when negative, the lithium ion of electrolytic solution passes through hole, thereby arrives electrochromic film easily and reposefully.So, reduction reaction steadily and promptly takes place in electrochromic film, electrochromic film is by steady and promptly painted.
In the above-described configuration, formation can be set to, described reduction reaction compensating unit comprises the anionic reactive film, described anionic reactive film forms and is arranged on the conductive reflecting film side of described conducting film by electric conductive polymer or redox polymers, and described anionic reactive film is by owing to apply the negative ion institute oxidation of described voltage towards described conducting film side shifting.
According to above-mentioned formation, in electrochromic film, be formed with along the thickness direction of electrochromic film a plurality of fine hole portion at the conductive reflecting film side opening.So, because the surface area of electrochromic film increases, thus when apply voltage make conducting film for just and conductive reflecting film when bearing, reduction reaction steadily and promptly takes place in electrochromic film, electrochromic film is by steady and promptly painted.
In above-mentioned first scheme, formation can be set to, and in described conductive reflecting film, is formed with a plurality of fine through hole that connects described conductive reflecting film at the thickness direction of described conductive reflecting film.
According to above-mentioned formation,, reduction reaction make first conductive reflecting film that constitutes conductive reflecting film and electric conductivity diaphragm for negative so that electrochromic film when painted, applies voltage when being taken place.
Form that more corrosion-resistant material forms by comparing more with the material that constitutes first conductive reflecting film towards the electric conductivity diaphragm of electrolytic solution side than first conductive reflecting film.Therefore, first conductive reflecting film is protected by the electric conductivity diaphragm, and first conductive reflecting film becomes and more is difficult to be corroded.As a result, first conductive reflecting film can be chronically with the mode reflected light of excellence.In addition; because first conductive reflecting film more is difficult to be corroded because of being protected to become by the electric conductivity diaphragm, thus can make first conductive reflecting film itself thinner, so; even when being provided with the electric conductivity diaphragm, the gross thickness of conductive reflecting film does not change thick yet.
In above-mentioned first scheme, formation can be set to, and in described conductive reflecting film, is formed with a plurality of fine through hole that connects described conductive reflecting film at the thickness direction of described conductive reflecting film.
According to above-mentioned formation, make the electric conductivity diaphragm of protection first conductive reflecting film become second conductive reflecting film of reflection from the light of the first conductive reflecting film side.As a result, even the part of light is owing to making thinner first conductive reflecting film that sees through of first conductive reflecting film, this light that has seen through also can be reflected at the second conductive reflecting film place.
In addition; thereby cover whole first conductive reflecting film from the electrolytic solution side and make the surrounding edge portion position situation more toward the outer side of second conductive reflecting film than first conductive reflecting film in that second conductive reflecting film is set; not only second conductive reflecting film improves to the protective value of first conductive reflecting film; and; because the part of second conductive reflecting film is positioned at the outside of the surrounding edge portion of first conductive reflecting film; even therefore in the outside of first conductive reflecting film, light also can be reflected.
According to the tenth scheme of the present invention, formation is set to, described conductive reflecting film comprises: have first conductive reflecting film of electric conductivity, described first conductive reflecting film is formed on a side of the thickness direction of described electrochromic film, and reflection has seen through the light of described electrochromic film; With the electric conductivity diaphragm with electric conductivity, described electric conductivity diaphragm is formed on a side opposite with described electrochromic film of described first conductive reflecting film, and corrosion-resistant material forms by comparing more with the material that constitutes described first conductive reflecting film.
According to above-mentioned formation, reflected by optical reflection film through ELD, electrochromic film and lithium ion light through film.
In addition, when apply voltage make conducting film for just and ELD when negative, the lithium ion that is encapsulated in the electrolytic solution between conducting film and the optical reflection film is towards the electrochromic film side shifting.Because lithium ion is towards the electrochromic film side shifting, so electrochromic film carries out reduction reaction, electrochromic film is owing to this reduction reaction is colored.Because electrochromic film is colored in this way, so the transmitance of the light in the electrochromic film reduces.
And, in EC mirror of the present invention, though optical reflection film by silver or contain silver alloy and forms, the lithium ion that silver-colored diffusion to electrochromic film is set between optical reflection film and the electrochromic film limits through film.So, can prevent or the silver-colored generation that is diffused into the caused problem of electrochromic film of inhibition effectively.
In above-mentioned the tenth scheme, formation can be set to, and described electric conductivity diaphragm comprises second conductive reflecting film with electric conductivity, and described second conductive reflecting film reflection is from the light of the described first conductive reflecting film side.
According to above-mentioned formation, when apply voltage make conducting film for just and ELD when negative, the negative ion of electrolytic solution moves towards a side (promptly towards the carbon film side) opposite with electrochromic film, and negative ion is stored in the carbon film.Carbon film is formed and contains activated charcoal.Because activated charcoal porous thereby have high surface area is so it can store many negative ion.So,, reduction reaction is taken place fully even the above-mentioned voltage that is applied to conducting film and optical reflection film is lower.And, owing in this way even with low voltage reduction reaction is taken place, after applying the voltage end, electrochromic film is easily decoloured.
In above-mentioned the tenth scheme, formation can be set to, and described conducting film is by silver or contain silver alloy and form; Described electrolytic solution is formed the negative ion that comprises difficulty soluble salt, when apply voltage make described conducting film for just and described first conductive reflecting film and described electric conductivity diaphragm when negative, the ionic reaction of the negative ion of described difficulty soluble salt and the silver that forms described conducting film; Described EC mirror also comprises separates out film, the described film of separating out is formed by described difficulty soluble salt, and be arranged on the electric conductivity diaphragm side of described conducting film, and precipitate is separated out, and described precipitate is by owing to apply described voltage towards the reaction formation between the ion of the negative ion of the described difficulty soluble salt of described conducting film side shifting and the silver that constitutes described conducting film; And described reduction reaction compensating unit comprises the silver that forms described conducting film, negative ion and the described film of separating out that constitutes described electrolytic solution.
According to above-mentioned formation, when apply voltage make conducting film for just and ELD when negative, the negative ion of electrolytic solution is towards the anionic reactive film side shifting that is formed by electric conductive polymer or redox polymers, the anionic reactive film is by the oxidation of negative ion institute.In this way, owing to the anionic reactive film that forms by electric conductive polymer or redox polymers, so many negative ion are fed in the oxidation of anionic reactive film, therefore, even the above-mentioned voltage that is applied to conducting film and conductive reflecting film is lower, reduction reaction is taken place fully.And, owing in this way even with low voltage reduction reaction is taken place, after applying the voltage end, electrochromic film is easily decoloured.
In above-mentioned the tenth scheme, formation can be set to, and in described conductive reflecting film, is formed with a plurality of fine through hole that connects described conductive reflecting film at the thickness direction of described conductive reflecting film.
When apply voltage make conducting film for just and ELD when negative, the lithium ion that is encapsulated in the electrolytic solution between conducting film and the optical reflection film is towards the electrochromic film side shifting.Because lithium ion is towards the electrochromic film side shifting, so electrochromic film carries out reduction reaction, electrochromic film is owing to this reduction reaction is colored.Because electrochromic film is colored in this way, so the transmitance of the light in the electrochromic film reduces.
When applying voltage as mentioned above, the negative ion that constitutes the difficulty soluble salt of electrolytic solution moves to the conducting film side.The ionic reaction of the negative ion of these difficulty soluble salts and the silver that constitutes conducting film, and separate out separating out on the film at the difficulty soluble salt of the conductive reflecting film side that is arranged on conducting film.
In this way, since conducting film and separate out the film place can make with electrochromic film in the corresponding oxidation reaction of reduction reaction take place fully, so, even the above-mentioned voltage that is applied to conducting film and conductive reflecting film is lower, reduction reaction is taken place fully.And, owing in this way even with low voltage reduction reaction is taken place, after applying the voltage end, electrochromic film is easily decoloured.
In above-mentioned the tenth scheme, formation can be set to, and in described electrochromic film, is formed with along the thickness direction of the described electrochromic film a plurality of fine hole portion at described conductive reflecting film side opening.
According to above-mentioned formation, optical reflection film is electrically connected to ELD.As a result, when applying voltage, by silver or contain the optical reflection film that silver alloy constitutes and also play electrode.
As mentioned above, in EC mirror of the present invention,, also can make electrochromic film painted fully even when not applying big voltage.
And, in EC mirror of the present invention, be difficult to take place as the deterioration that corrosion caused of the conductive reflecting film of optical reflection film.

Claims (31)

1. an EC mirror is characterized in that, described EC mirror comprises:
Electrochromic film, described electrochromic film is colored owing to carrying out reduction reaction;
Conductive reflecting film with electric conductivity, described conductive reflecting film are formed on the side of thickness direction of described electrochromic film and the light that reflection has seen through described electrochromic film;
Conducting film with electric conductivity, described conducting film are arranged on the side of thickness direction of described electrochromic film and a side opposite with described electrochromic film of described conductive reflecting film;
Electrolytic solution, described electrolytic solution comprises lithium ion, and be encapsulated between described conductive reflecting film and the described conducting film, wherein, since apply voltage make described conducting film for just and described conductive reflecting film for bearing, so described lithium ion is towards described electrochromic film side shifting, and supply to the reduction reaction of described electrochromic film; With
The reduction reaction compensating unit, described reduction reaction compensating unit by storage be in the electric charge that applies described voltage status or by with described electrolytic solution in negative ion carry out oxidation reaction, compensate described reduction reaction.
2. EC mirror as claimed in claim 1 is characterized in that, described reduction reaction compensating unit comprises the carbon film with electric conductivity, and described carbon film is formed on the conductive reflecting film side of described conducting film and contains activated charcoal.
3. electrochromic film as claimed in claim 2 is characterized in that, in described conductive reflecting film, is formed with a plurality of fine through hole that connects described conductive reflecting film at the thickness direction of described conductive reflecting film.
4. EC mirror as claimed in claim 3 is characterized in that, in described electrochromic film, is formed with along the thickness direction of the described electrochromic film a plurality of fine hole portion at described conductive reflecting film side opening.
5. EC mirror as claimed in claim 2 is characterized in that, described conductive reflecting film comprises:
First conductive reflecting film with electric conductivity, described first conductive reflecting film is formed on a side of the thickness direction of described electrochromic film, and reflection has seen through the light of described electrochromic film; With
Electric conductivity diaphragm with electric conductivity, described electric conductivity diaphragm are formed on a side opposite with described electrochromic film of described first conductive reflecting film, and corrosion-resistant material forms by comparing more with the material that constitutes described first conductive reflecting film.
6. EC mirror as claimed in claim 5 is characterized in that, described electric conductivity diaphragm comprises second conductive reflecting film with electric conductivity, and described second conductive reflecting film reflection is from the light of the described first conductive reflecting film side.
7. EC mirror as claimed in claim 1, it is characterized in that, described reduction reaction compensating unit comprises the anionic reactive film, described anionic reactive film forms and is arranged on the conductive reflecting film side of described conducting film by electric conductive polymer or redox polymers, and described anionic reactive film is by owing to apply the negative ion institute oxidation of described voltage towards described conducting film side shifting.
8. EC mirror as claimed in claim 7 is characterized in that, in described conductive reflecting film, is formed with a plurality of fine through hole that connects described conductive reflecting film at the thickness direction of described conductive reflecting film.
9. EC mirror as claimed in claim 8 is characterized in that, in described electrochromic film, is formed with along the thickness direction of the described electrochromic film a plurality of fine hole portion at described conductive reflecting film side opening.
10. EC mirror as claimed in claim 7 is characterized in that, described conductive reflecting film comprises:
First conductive reflecting film with electric conductivity, described first conductive reflecting film is formed on a side of the thickness direction of described electrochromic film, and reflection has seen through the light of described electrochromic film; With
Electric conductivity diaphragm with electric conductivity, described electric conductivity diaphragm are formed on a side opposite with described electrochromic film of described first conductive reflecting film, and corrosion-resistant material forms by comparing more with the material that constitutes described first conductive reflecting film.
11. EC mirror as claimed in claim 10 is characterized in that, described electric conductivity diaphragm comprises second conductive reflecting film with electric conductivity, and described second conductive reflecting film reflection is from the light of the described first conductive reflecting film side.
12. EC mirror as claimed in claim 1 is characterized in that:
Described conducting film is by silver or contain silver alloy and form;
Described electrolytic solution is formed the negative ion that comprises difficulty soluble salt, when apply voltage make described conducting film for just and described first conductive reflecting film and described electric conductivity diaphragm when negative, the ionic reaction of the negative ion of described difficulty soluble salt and the silver that forms described conducting film;
Described EC mirror also comprises separates out film, the described film of separating out is formed by described difficulty soluble salt, and be arranged on the electric conductivity diaphragm side of described conducting film, and precipitate is separated out, and described precipitate is by owing to apply described voltage towards the reaction formation between the ion of the negative ion of the described difficulty soluble salt of described conducting film side shifting and the silver that constitutes described conducting film; And
Described reduction reaction compensating unit comprises the described silver that forms described conducting film, described negative ion and the described film of separating out that constitutes described electrolytic solution.
13. EC mirror as claimed in claim 12 is characterized in that, in described conductive reflecting film, is formed with a plurality of fine through hole that connects described conductive reflecting film at the thickness direction of described conductive reflecting film.
14. EC mirror as claimed in claim 13 is characterized in that, in described electrochromic film, is formed with along the thickness direction of the described electrochromic film a plurality of fine hole portion at described conductive reflecting film side opening.
15. EC mirror as claimed in claim 12 is characterized in that, described conductive reflecting film comprises:
First conductive reflecting film with electric conductivity, described first conductive reflecting film is formed on a side of the thickness direction of described electrochromic film, and reflection has seen through the light of described electrochromic film; With
Electric conductivity diaphragm with electric conductivity, described electric conductivity diaphragm are formed on a side opposite with described electrochromic film of described first conductive reflecting film, and corrosion-resistant material forms by comparing more with the material that constitutes described first conductive reflecting film.
16. EC mirror as claimed in claim 15 is characterized in that, described electric conductivity diaphragm comprises second conductive reflecting film with electric conductivity, and described second conductive reflecting film reflection is from the light of the described first conductive reflecting film side.
17. EC mirror as claimed in claim 5 is characterized in that:
Described electrolytic solution contains reaction material, and described reaction material can be by neutral molecule or the oxidation of negative ion institute, and owing to apply voltage make described conducting film for just and described first conductive reflecting film and described electric conductivity diaphragm be the negative oxidation reaction of carrying out; And
Described reduction reaction compensating unit comprises described reaction material.
18. EC mirror as claimed in claim 1 is characterized in that, in described conductive reflecting film, is formed with a plurality of fine through hole that connects described conductive reflecting film at the thickness direction of described conductive reflecting film.
19. EC mirror as claimed in claim 18 is characterized in that, in described electrochromic film, is formed with along the thickness direction of the described electrochromic film a plurality of fine hole portion at described conductive reflecting film side opening.
20. EC mirror as claimed in claim 1 is characterized in that, described conductive reflecting film comprises:
First conductive reflecting film with electric conductivity, described first conductive reflecting film is formed on a side of the thickness direction of described electrochromic film, and reflection has seen through the light of described electrochromic film; With
Electric conductivity diaphragm with electric conductivity, described electric conductivity diaphragm are formed on a side opposite with described electrochromic film of described first conductive reflecting film, and corrosion-resistant material forms by comparing more with the material that constitutes described first conductive reflecting film.
21. EC mirror as claimed in claim 20 is characterized in that, described electric conductivity diaphragm comprises second conductive reflecting film with electric conductivity, and described second conductive reflecting film reflection is from the light of the described first conductive reflecting film side.
22. EC mirror as claimed in claim 20, wherein, described reduction reaction compensating unit comprises the carbon film with electric conductivity, and described carbon film is formed on the conductive reflecting film side of described conducting film and contains activated charcoal.
23. EC mirror as claimed in claim 20, it is characterized in that, described reduction reaction compensating unit comprises the anionic reactive film, described anionic reactive film forms and is arranged on the conductive reflecting film side of described conducting film by electric conductive polymer or redox polymers, and described anionic reactive film is by owing to apply the negative ion institute oxidation of described voltage towards described conducting film side shifting.
24. EC mirror as claimed in claim 20 is characterized in that:
Described conducting film is by silver or contain silver alloy and form;
Described electrolytic solution is formed the negative ion that comprises difficulty soluble salt, when apply voltage make described conducting film for just and described first conductive reflecting film and described electric conductivity diaphragm when negative, the ionic reaction of the negative ion of described difficulty soluble salt and the silver that forms described conducting film;
Described EC mirror also comprises separates out film, the described film of separating out is formed by described difficulty soluble salt, and be arranged on the electric conductivity diaphragm side of described conducting film, and precipitate is separated out, and described precipitate is by owing to apply described voltage towards the reaction formation between the ion of the negative ion of the described difficulty soluble salt of described conducting film side shifting and the silver that constitutes described conducting film; And
Described reduction reaction compensating unit comprises the described silver that forms described conducting film, described negative ion and the described film of separating out that constitutes described electrolytic solution.
25. EC mirror as claimed in claim 20, wherein:
Described electrolytic solution contains reaction material, and described reaction material can be by neutral molecule or the oxidation of negative ion institute, and owing to apply voltage make described conducting film for just and described first conductive reflecting film and described electric conductivity diaphragm be the negative oxidation reaction of carrying out; And
Described reduction reaction compensating unit comprises described reaction material.
26. EC mirror as claimed in claim 20 is characterized in that, in described electrochromic film, is formed with along the thickness direction of the described electrochromic film a plurality of fine hole portion at described conductive reflecting film side opening.
27. an EC mirror is characterized in that, described EC mirror comprises:
ELD, described ELD can printing opacities and are had electric conductivity;
Electrochromic film, described electrochromic film are formed on a side of the thickness direction of described ELD, and are colored owing to carrying out reduction reaction;
Optical reflection film, described optical reflection film is by silver or contain silver alloy and forms, and reflection is through the light of described ELD and described electrochromic film;
Transparent lithium ion sees through film, and described lithium ion sees through film and is arranged between described electrochromic film and the described optical reflection film, and can see through lithium ion and the diffusion of restriction silver from described optical reflection film side to described electrochromic film side;
What the conducting film with electric conductivity, described conducting film were arranged on the side of thickness direction of described ELD and described optical reflection film sees through the opposite side of film with described lithium ion;
Electrolytic solution, described electrolytic solution comprises lithium ion, and be encapsulated between described optical reflection film and the described conducting film, wherein, since apply voltage make described conducting film for just and described ELD for bearing, so described lithium ion is towards described electrochromic film side shifting, and supply to the reduction reaction of described electrochromic film; With
The reduction reaction compensating unit, described reduction reaction compensating unit by storage be in the electric charge that applies described voltage status or by with described electrolytic solution in negative ion carry out oxidation reaction, compensate described reduction reaction.
28. EC mirror as claimed in claim 27 is characterized in that, described reduction reaction compensating unit comprises the carbon film with electric conductivity, and described carbon film is formed on the conductive reflecting film side of described conducting film and contains activated charcoal.
29. EC mirror as claimed in claim 27, it is characterized in that, described reduction reaction compensating unit comprises the anionic reactive film, described anionic reactive film forms and is arranged on the conductive reflecting film side of described conducting film by electric conductive polymer or redox polymers, and described anionic reactive film is by owing to apply the negative ion institute oxidation of described voltage towards described conducting film side shifting.
30. EC mirror as claimed in claim 27 is characterized in that:
Described conducting film is by silver or contain silver alloy and form;
Described electrolytic solution is formed the negative ion that comprises difficulty soluble salt, when apply voltage make described conducting film for just and described ELD when negative, the ionic reaction of the negative ion of described difficulty soluble salt and the silver that forms described conducting film;
Described EC mirror also comprises separates out film, the described film of separating out is formed by described difficulty soluble salt, and be arranged on the electric conductivity diaphragm side of described conducting film, and precipitate is separated out, and described precipitate is by owing to apply described voltage towards the reaction formation between the ion of the negative ion of the described difficulty soluble salt of described conducting film side shifting and the silver that constitutes described conducting film; And
Described reduction reaction compensating unit comprises the described silver that forms described conducting film, described negative ion and the described film of separating out that constitutes described electrolytic solution.
31. EC mirror as claimed in claim 27, wherein, described optical reflection film is electrically connected to described ELD.
CN 200810124993 2007-06-26 2008-06-25 Electrochromic mirror Expired - Fee Related CN101334568B (en)

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JP2007167913A JP2009008750A (en) 2007-06-26 2007-06-26 Electrochromic mirror
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CN112882304A (en) * 2021-01-22 2021-06-01 维沃移动通信有限公司 Cover plate assembly and electronic equipment

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