JPS6313022A - Antidazzle mirror - Google Patents

Abstract

PURPOSE:To eliminate the dead angle by an inside mirror by providing a mirror which is semitransparent and is variable in reflectivity and transmittance. CONSTITUTION:An electrochromic material layer 2 consisting of a polytriphenyl amine and a porous reflective layer 3 consisting of Pd are provided to one of a pair of transparent substrates 1 and a transparent electrode 5 and an electrochromic material layer 4 consisting of WO3, etc., are provided on the other substrate 1. The substrates are fixed by disposing the layers 3 and the layer 4 to face each other. An electrolyte 6 is sealed in the formed space. The reflectivity and transmittance variable mirror is thereby constituted. The scenes behind the mirror is discriminatable in the highly reflective state and the antidazzle effect for the head light of succeeding cars is obtd. in the nighttime.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an anti-glare mirror with variable reflection or transmittance.

(Prior Art) Examples of conventional anti-glare inside mirrors (liquid crystal type) include those shown in FIGS. 3 to 5.

Here, 12 is an optical sensor, 13 is a switch, 14 is a mirror housing, 15 is a stay, 16 is a liquid crystal anti-glare mirror, 17 is a circuit board, and 18 is a pivot. As shown in detail in FIG. 5, this liquid crystal anti-glare mirror has a transparent substrate 1 provided with a transparent electrode 5 and a substrate 20 provided with a reflective electrode 19 arranged in parallel so that the electrodes face each other, and the surrounding area is surrounded by a sealing material 8. The liquid crystal 21 is sealed in the space obtained.
The state of the liquid crystal is changed by applying an electric field between the transparent electrode 5 and the reflective electrode 19, and the reflectance of the reflective electrode is controlled by utilizing the fact that the light transmittance changes due to this effect.

(Problems to be Solved by the Invention) However, in such conventional anti-glare mirrors, the portion of the mirror 22 is unretractable, as shown in FIGS. 6 and 7 for the inside mirror 22 of an automobile. There was a problem that the blind spot was 23, and the visibility of the front force was slightly worsened by this amount.

(Means for Solving the Problems) The present invention solves the above problems by using a variable reflectance and transmittance mirror as an anti-glare mirror.

That is, the anti-glare mirror of the present invention includes a pair of transparent substrates, a variable light transmittance material held between the transparent substrates and whose light transmittance changes depending on an applied voltage, and a transparent electrode for applying a voltage to the variable light transmittance material. This is an anti-glare mirror having a porous layer that semi-transmits light. The present invention will be explained in more detail below. In the following description, an electrochromic material is used as the light transmission rate variable material. That is, a first electrochromic material layer and a porous layer that reflects light that comes into contact with the first electrochromic material layer are provided on the first substrate of a pair of transparent substrates, and a conductive material layer is provided on the second substrate. It is obtained by comprising a transparent electrode and a second electrochromic material layer in contact with the conductive transparent electrode, overlapping each electrochromic material layer with a spacer in between so as to face each other, and fixing the periphery with an adhesive. In an anti-glare mirror in which an electrolyte is sealed in a space, a conjugated polymer film is used as the first electrochromic material layer, and a transition metal oxide film is used as the second electrochromic material layer.

Examples of the conjugated polymer material as the first electrochromic substance used in this invention include polytriphenylamine, polyparaphenylene, poly(N-methylpyrrole), polyaniline, and the like. At the time of film formation, these conjugated polymer materials are colorless and transparent in a reduced state or have low coloring strength, and when oxidized, the transition absorption energy of π electrons due to double bonds and unpaired electrons changes, resulting in visible It is said that the absorption spectrum of light changes.

In particular, a polymer coating having a 4,4',4''-triphenylamine structure or its derivative structure as a repeating unit is a suitable material because it becomes almost completely colorless and transparent in a reduced state and has a low driving voltage. .

As a method for forming this polymer film, there are the following methods.

(a) 4, 4 represented by the following formula (in the formula, x, y, and z represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an acyl group, an allyl group, a vinyl group, or a vinylidene group)
',4'-) Riphenylamine or its derivative is formed into a film on an electrode and polymerized by reacting with an oxidizing agent such as iodine, antimony pentafluoride, arsenic pentafluoride, or ferric oxide, Fix it on the electrode.

(b) Synthesize a polymer soluble in a solvent by polymerizing the monomer, and form a film of this polymer on an electrode,
A crosslinking reaction is performed by reacting with the same oxidizing agent as in (a), and it is fixed on the electrode.

(c) The monomers or a solvent-soluble polymer synthesized from these monomers are dissolved in an electrolyte and polymerized on the electrode by electropolymerization.

(d) As x, y, and z of the monomers, a derivative having unsaturated carbon such as an allyl group or a vinyl group is synthesized, this derivative is formed into a film on an electrode, and a polymerization reaction is caused by heating or ultraviolet irradiation. Raise it up and fix it on the electrode.

Examples of the transition metal oxide as the second electrochromic substance include WO, Nb, and O.

CrzOi+ TazOs+ Tilt, FezO+
+AgO etc. are mentioned.

In the anti-glare mirror of the present invention, the first electrochromic material layer provided between a pair of transparent substrates is composed of a conjugated polymer film, the second electrochromic material layer is composed of a transition metal oxide film, and the first It can be fabricated in the same manner as a conventional mirror, except that a porous reflective layer is formed on top of the electrochromic material layer.

FIG. 1 is a diagram showing an anti-glare mirror of the first example of the present invention manufactured in this manner, in which 5 is an ITO (Indium
1 is a transparent substrate such as a glass substrate, 8 is a sealing material such as an epoxy adhesive, 2
is a first electrochromic material layer such as polytriphenylamine, 3 is a porous reflective layer such as a palladium (Pd) thin film, 4 is a second electrochromic material layer such as 1, and 6 is 1 mol/l. A solution of LiClO4 in propylene carbonate (PC).

FIG. 2 shows a second example of an anti-glare mirror, in which a third electrode 9 and a fourth electrode 10 are further provided as shown in the figure, and the first electrochromic material layer is connected to the first electrochromic material layer via a power source 11, respectively. 2 and the second electrochromic substance N4
The light transmittance is connected to the light source and colored and erased separately.In this way, only the transmittance can be changed independently.

In this invention, any material can be used as the porous reflective layer as long as it is electrochemically stable and can provide a mirror surface, such as platinum (Pt), palladium (Pd), gold ( ＾U) etc. ``Also, as an electrolyte, LiCl0a+ LiBF, LiPF, etc.

Acetonitrile, propylene carbonate, N
.

Common solvents or mixed solvents such as N'-dimethylformamide and water are used.

(Example) This invention will be explained below with reference to Examples.

EXAMPLE 1 The electrochromic device shown in FIG. 1 was prepared by the method shown below.

(a) As the first electrochromic material layer 2, 4
．． A solution in which a polymer having an average molecular weight of about 2,000 obtained by polymerizing 4'-dichlorotriphenylamine using a Grignard reaction was dissolved in chloroform at a concentration of 15 g/l was spun onto the surface of the transparent substrate 1. code (1,500 rpm, 60 seconds), then placed in a deaerated container, then the container was filled with I2 vapor and heated at 100° C. for 3 hours to obtain a thin film of polytriphenylamine.

(0) On the polytriphenylamine thin film thus obtained, Pd was deposited as a porous reflective layer 3 to a thickness of 500 mm (substrate heating 80°C, vacuum level 5 x 10-s torr). ), the deposition rate was 1088 ec).

(c) As the second electrochromic material layer 4, WO was vapor-deposited on the electrode 5 on the transparent substrate 1 to a thickness of 4,000 mm (substrate heating 80°C, vacuum degree 5 x 1).
The film was formed at a deposition rate of 10 persons/5 ec).

(d) Glass beads having a diameter of 40 μm were scattered as spacers 7 on the polytriphenylamine side of the substrate (El) at a rate of about 15 beads/cm 2 .

(N) (C) Board oath 0. An epoxy adhesive was applied as a sealing material 8 by screen printing around the sides, except for the area where the electrolyte solution was injected.

(f) The substrates of (d) and (f) were placed one on top of the other so that the electrochromic material layers faced each other, and the adhesive was cured while applying pressure.

()) Inlet of the cell prepared in (f) (not shown)
1 moJ/j with water added as electrolyte 6! Li
After a propylene carbonate solution of ClO4 was injected according to a liquid crystal injection method, the injection port was sealed with an epoxy adhesive to form an electrolyte layer 19 containing about 3% water.

4. The conjugated polymer film obtained based on 4'-dichlorotriphenylamine is in a reduced state and colorless and transparent when it is formed; therefore, it is in an oxidized state and is colorless and transparent when it is formed. When combined with item 10, it becomes a half mirror when assembled.

In order to examine the redox reaction of this mirror, FIG. 8 shows the results of measurements made using a cyclic voltamodrum with the WOi side as the counter electrode at an applied voltage sweep rate of 10 mV/sec. The working electrode in this case is polytriphenylamine (1
02cm”), counter electrode WO, (102cm2), electrolyte 1 mo j! / I LiCIO4/PC+ 3
%820.

This element exhibits good electrocomic properties; in an oxidation reaction, the color changes to dark blue and the reflectance and transmittance decrease at approximately 1.3 V [vs WO:+], and on the other hand, when reduced, it changes to approximately 0.3 V. (vs WOi) it returned to colorless.

Also, the relationship between the amount of injected charge and the degree of coloring (j!og (1/reflectance) or Aog (1/transmittance)) when viewed from the polytriphenylamine side of this mirror is for reflection and transmission. The cases are as shown in FIGS. 9 and 10, respectively, and it can be seen that the reflectance and transmittance variable mirrors are obtained.

In other words, in a highly reflective state, the transmittance is about 8%, so the scenery behind the mirror can be distinguished, and at night, the reflectance is lowered to provide an anti-glare effect against the headlights of following cars. be.

Furthermore, since the amount of charge injected is proportional to the degree of coloring, it can be seen that by changing the thickness of the conjugated polymer film, the reflectance during coloring can be changed accordingly. It can also be seen that by controlling the amount of charge injected, any desired reflectance or transmittance can be obtained.

4.4'-Dichlorotriphenylamine was used instead of the polymer obtained by polymerizing 4,4'-dichlorotriphenylamine in Example 1.
A mirror similar to that of Example 1 was obtained by using a polymer obtained by polymerizing dibrome-4#-methyltriphenylamine (average molecular weight approximately 3.000).

In Example 1, instead of the polymer obtained by polymerizing 4,4'-dichloroto IJ phenylamine, 4.4
Polymer obtained by polymerizing '-dibromo-4#-methoxytriphenylamine (average molecular weight approximately 5.000)
A similar mirror was obtained using

Example 1 In Example 1, a similar mirror was obtained by using a porous reflective layer obtained by electron beam evaporation of PT instead of Pd0. In the above examples, the observation results from the second electrochromic material layer side were also the same as those from the first electrochromic material layer side.

In the above description, an electrochromic material was used as an example of the optically variable material, but the same effect can be obtained by using a liquid crystal.

As mentioned above, the mirror of this invention was considered to be sufficiently practical.

(Effects of the Invention) As explained above, the anti-glare mirror of the present invention is a semi-transmissive mirror with variable reflectance and transmittance, so it can eliminate the blind spot caused by inside mirrors, and it can be used automatically at night. The effect is that it can also function as an anti-glare mirror.

[Brief explanation of the drawing]

1 and 2 are respectively sectional views of the electrochromic anti-glare mirror of the present invention, FIG. 3 is a perspective view of a conventional anti-glare inside mirror, and FIG. 4 is a sectional view of the anti-glare mirror of FIG. Figure 5 is a cross-sectional view of a liquid crystal element, Figures 6 and 7 are illustrations of blind spots caused by an inside mirror installed in a car, and Figure 8 is a cyclic portameter showing the electrochemical characteristics of the element in Figure 1. gram diagram, Figure 9 is a diagram showing the relationship between the transmissivity of the element in Figure 1 and the amount of applied charge, Figure 10 is a diagram showing the relationship between the transmittance of the element in Figure 1 and the amount of applied charge. It is a line diagram. 1... Transparent substrate 2... First electrochromic material layer 3... Porous reflective layer 4... Second electrochromic material layer 5... Transparent electrode 6... Electrolyte 7. ··Spacer
8...Sealing material 9...Third electrode 1
0...4th pole 11...power supply 12.
...Light sensor-13...Switch 14...
・Mirror housing 15...stay 16
...Liquid crystal anti-glare mirror 17...Circuit board 1
8... Pivot 19... Reflective electrode 20.
...Substrate 21...Liquid crystal 22...Inside mirror 23...Blind spot patent applicant Nissan Motor Co., Ltd.Figure 1Figure 2Figure 3Figure 4Figure 4 2-f Figure 5Figure 6Figure 7 Figure 9

Claims (1)

[Claims] 1. A pair of transparent substrates, a variable light transmittance material held between the transparent substrates whose light transmittance changes depending on an applied voltage, a transparent electrode that applies voltage to the variable light transmittance material, and a transparent electrode that semi-transmits light. Anti-glare mirror with a porous layer.