WO2014162909A1 - 有色防曇鏡 - Google Patents
有色防曇鏡 Download PDFInfo
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- WO2014162909A1 WO2014162909A1 PCT/JP2014/058031 JP2014058031W WO2014162909A1 WO 2014162909 A1 WO2014162909 A1 WO 2014162909A1 JP 2014058031 W JP2014058031 W JP 2014058031W WO 2014162909 A1 WO2014162909 A1 WO 2014162909A1
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- WIPO (PCT)
- Prior art keywords
- layer
- reflectance
- colored
- mirror
- fog mirror
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0808—Mirrors having a single reflecting layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R1/00—Optical viewing arrangements; Real-time viewing arrangements for drivers or passengers using optical image capturing systems, e.g. cameras or video systems specially adapted for use in or on vehicles
- B60R1/02—Rear-view mirror arrangements
- B60R1/06—Rear-view mirror arrangements mounted on vehicle exterior
- B60R1/0602—Rear-view mirror arrangements mounted on vehicle exterior comprising means for cleaning or deicing
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation
Definitions
- the present invention relates to a colored antifogging mirror with a surface mirror that has a blue or green reflection color and has antifogging properties, and improves the photocatalytic performance as compared with conventional products, while the viewer's line of sight faces the mirror surface. This is a reduction in color misregistration due to changes in the angle to be performed.
- FIG. 2 schematically shows a laminated structure of the colored anti-fog mirror 10 that has been put to practical use.
- the colored anti-fog mirror 10 is configured by sequentially laminating a reflective layer 14, a photocatalyst layer 16, and a hydrophilic layer 18 on the surface of a substrate 12.
- the base 12 is made of a glass substrate such as soda glass.
- the reflective layer 14 is made of a metal such as Cr.
- Photocatalytic layer 16 is composed of TiO 2.
- the hydrophilic layer 18 is made of porous SiO 2 .
- the film thickness of the photocatalyst layer 16 is set to about 75 nm in order to make the reflected color blue.
- the colored antifogging mirror 10 generates a blue or green reflection color by interference of reflected light in each layer.
- the hydrophilic layer 18 provides antifogging properties.
- the anti-fogging property of the hydrophilic layer 18 is maintained by decomposing and removing the organic matter adhering to the surface of the hydrophilic layer 18 by the photocatalytic action of the photocatalytic layer 16.
- the colored anti-fog mirror having such a structure is described in Patent Documents 1 and 2 below.
- the thickness of the TiO 2 film 10 is set to 150 nm or less so that it can be easily observed in the visible light range. It is preferable to set so as to have one peak ”(the description, 0023).
- the film thickness of the photocatalytic film 16 has a spectral reflection spectrum such that the reflected light of the colored antifogging mirror 10 satisfies the above-described conditions.
- the film thickness is preferably 50 to 130 nm, and if the film thickness of the photocatalytic film 16 is less than the lower limit, the spectral reflection is within the visible light reflection range.
- the above upper limit is exceeded, multiple spectral reflection peaks appear in the visible light reflection region, and other colors overlap with each other, and the color tone tends to change depending on the angle of the line of sight. There is a description of "Yes" (specification 0038).
- the angle at which the viewer's line of sight faces the mirror surface (hereinafter referred to as “line of sight angle”).
- the thickness of the photocatalyst TiO 2 layer is made thin in order to prevent color shift (change in color tone with respect to the color tone when the line-of-sight angle is 0 degree) due to a change in the angle facing the mirror surface from the front. It was recommended. However, it has been found that when the film thickness of the photocatalytic TiO 2 layer becomes thinner than 140 nm, there is a problem in durability against a water-repellent washing car that has been rapidly spread in recent years.
- the water repellent contained in the water repellent car wash used in the water repellent car is mainly composed of a silicone resin, it cannot be removed by photocatalysis when it adheres to the mirror surface. For this reason, the water repellent is accumulated on the surface of the mirror while the water-repellent car wash is repeated, and the photocatalytic performance is lowered. In this case, if the film thickness of the photocatalytic TiO 2 layer is large, the photocatalytic performance is sufficient, so even if some water repellent is accumulated on the surface of the mirror, the dirt adhering to it is decomposed to restore hydrophilicity. Can be made.
- the thickness of the TiO 2 layer is thin, there is no room for photocatalytic performance, so even if a little water repellent is accumulated on the surface of the mirror, it becomes impossible to decompose the dirt attached on it. The hydrophilicity cannot be recovered.
- the present invention has been made in view of the above-mentioned points, and for a colored anti-fog mirror using a surface mirror having a blue or green reflection color and having anti-fogging properties, the line of sight is enhanced while improving the durability against a water-repellent car wash. It is an object of the present invention to provide a colored anti-fog mirror that reduces color shift due to a change in angle.
- This invention has a structure in which a reflective layer, a reflectance adjustment layer, a photocatalyst layer, and a hydrophilic layer are sequentially laminated on the surface of a substrate, and the photocatalyst layer is substantially composed of TiO 2 , and the film thickness of the photocatalyst layer Is 140 to 200 nm, the hydrophilic layer is substantially composed of porous SiO 2 , and thus the maximum value of reflectance in the visible light region exists at a wavelength of 430 to 560 nm, and the reflection color is blue or green.
- This is a colored anti-fog mirror that exhibits a system and has a ratio between the maximum value and the minimum value of the reflectance in the visible light region of 2 or more and 4 or less.
- the film thickness of the TiO 2 photocatalyst layer is increased, the photocatalytic performance is improved and the durability against the water-repellent car wash is improved. Further, when the thickness of the TiO 2 photocatalyst layer is increased, the reflectance in the visible light region is lowered, and the maximum value and the minimum value of the reflectance are generated in the visible light region so that the color shift due to the change in the viewing angle is noticeable. Become. On the other hand, in this invention, since the reflectance adjustment layer is disposed between the reflective layer and the photocatalyst layer, a decrease in the reflectance in the visible light region is suppressed, and the maximum and minimum values of the reflectance in the visible light region are suppressed.
- the present invention has the desired effect when the film thickness of the photocatalyst layer is about 140 to 200 nm, the photocatalytic effect does not increase so much when the film thickness of the photocatalyst layer exceeds a certain thickness. About 165 ⁇ 20 nm is practical. Moreover, the film thickness of a photocatalyst layer can also be made larger than 150 nm.
- the reflectance adjusting layer is substantially composed of a mixture of Al 2 O 3 and any one or more of Ta 2 O 5 , SnO 2 , and ZrO 2. it can.
- the volume percentage of Al 2 O 3 contained in the reflectance adjustment layer (hereinafter,% of content means volume percentage) is such that the reflectance adjustment layer is substantially composed of Al 2 O 3 and Ta 2. 50% or more and 95% or less when composed of a mixture of O 5 , and 30% or more and 90% or less when the reflectance adjustment layer is substantially composed of a mixture of Al 2 O 3 and SnO 2 ,
- the reflectance adjusting layer is substantially composed of a mixture of Al 2 O 3 and ZrO 2 , it can be 40% or more and 90% or less.
- the reflectance adjustment layer contains any of Ta 2 O 5 , SnO 2 , and ZrO 2 , it is possible to suppress a decrease in water resistance due to Al 2 O 3 . More specifically, when the reflectance adjustment layer is substantially composed of a mixture of Al 2 O 3 and Ta 2 O 5 , Al 2 O 3 contained in the reflectance adjustment layer is 50% or more (or Ta 2 When O 5 is 50% or less, a practically sufficient reflectance and color tone deviation can be reduced. Further, when Al 2 O 3 contained in the reflectance adjustment layer is 95% or less (or Ta 2 O 5 is 5% or more), practically sufficient water resistance can be obtained.
- the Al 2 O 3 contained in the reflectance adjusting layer is 70% or more (or Ta 2 O 5 30% or less) or 95% or less (or Ta 2 O 5 is 5% or more). According to this, when Al 2 O 3 contained in the reflectance adjustment layer is 70% or more, a further sufficient reflectance can be obtained, and an effect of further reducing color shift can be obtained.
- the reflectance adjustment layer is substantially composed of a mixture of Al 2 O 3 and SnO 2
- Al 2 O 3 contained in the reflectance adjustment layer is 30% or more (or SnO 2 is 70% or less). As a result, a practically sufficient reflectance and color tone shift can be reduced.
- Al 2 O 3 contained in the reflectance adjusting layer is 90% or less (or SnO 2 is 10% or more), practically sufficient water resistance can be obtained.
- the reflectance adjustment layer is substantially composed of a mixture of Al 2 O 3 and ZrO 2 , Al 2 O 3 contained in the reflectance adjustment layer is 40% or more (or ZrO 2 is 60% or less). As a result, a practically sufficient reflectance and color tone shift can be reduced. Further, when Al 2 O 3 contained in the reflectance adjusting layer is 90% or less (or ZrO 2 is 10% or more), practically sufficient water resistance can be obtained.
- the film thickness of the reflectance adjustment layer can be set to 35 to 85 nm, for example.
- FIG. 1 It is a schematic cross section which shows embodiment of the colored anti-fog mirror by this invention. It is a schematic cross section which shows the structure of the colored anti-fog mirror utilized conventionally. Is a diagram showing the relationship between the film thickness and the photocatalytic performance of TiO 2 photocatalyst layer. 3 is a chart showing an example of film forming conditions when the reflectance adjusting layer 20, the photocatalyst layer 16, and the hydrophilic layer 18 of the colored antifogging mirror of FIG. 1 are formed by vapor deposition. 6 is a chart showing main specifications of Examples 1 to 8 and Comparative Examples 1 to 4. It is a diagram which shows the spectral reflection spectrum in the visible light region of Example 1.
- FIG. 15A is a chart showing a maximum reflectance value, a minimum reflectance value, and a maximum / minimum reflectance ratio (referred to as a maximum reflectance value / a minimum reflectance value) in the visible light region according to the characteristics of FIG. 15A. It is a diagram which shows the spectral reflection spectrum in a visible light region when changing a gaze angle about Example 3.
- FIG. 16B is a chart showing a maximum reflectance value, a minimum reflectance value, and a maximum / minimum reflectance ratio in the visible light region according to the characteristics of FIG. 16A.
- FIG. 17B is a chart showing a maximum reflectance value, a minimum reflectance value, and a maximum / minimum reflectance ratio in the visible light region according to the characteristics of FIG. 17A. It is a diagram which shows the spectral reflection spectrum in a visible light region when changing a gaze angle about the comparative example 4.
- FIG. 18B is a chart showing a maximum reflectance value, a minimum reflectance value, and a maximum / minimum reflectance ratio in the visible light region according to the characteristics of FIG. 18A. It is a diagram which shows the spectral reflection spectrum in the visible light range of the conventional colored anti-fog mirror 10 shown in FIG. FIG.
- FIG. 3 is a diagram showing the results of a comparative test of the durability of the photocatalytic performance with respect to a water-repellent car wash for the colored antifogging mirror 11 of Examples 1 to 4 and the conventional colored antifogging mirror 10 of FIG. It is a diagram which shows the spectral reflection spectrum in the visible light region of Example 5. It is a diagram which shows the spectral reflection spectrum in the visible light region of Example 6. It is a diagram which shows the spectral reflection spectrum in the visible light region of Example 7. It is a diagram which shows the spectral reflection spectrum in the visible light region of Example 8.
- FIG. 1 schematically shows a laminated structure of a colored anti-fog mirror 11 according to the present invention.
- the colored anti-fog mirror 11 constitutes a mirror body portion of an outer mirror for vehicles.
- the colored anti-fog mirror 11 is configured by sequentially laminating a reflective layer 14, a reflectance adjustment layer 20, a photocatalyst layer 16, and a hydrophilic layer 18 on the surface of a substrate 12.
- the colored antifogging mirror 11 generates a blue or green reflection color by interference of reflected light in each layer.
- Each layer will be described.
- ⁇ Substrate 12 >>
- the substrate 12 is made of a glass substrate such as soda glass.
- the reflective layer 14 is made of a metal such as Cr.
- Photocatalyst layer 16 is composed of TiO 2.
- the thickness of the TiO 2 photocatalyst layer 16 is set to about 75 nm in order to make the reflected color blue.
- the colored antifogging mirror 11 of FIG. 1 sets the film thickness of the photocatalyst layer 16 to a thick film thickness of 140 to 200 nm in order to make the reflected color blue (or green).
- the photocatalyst layer 16 maintains the anti-fogging property of the hydrophilic layer 18 by decomposing and removing the organic matter adhering to the surface of the hydrophilic layer 18 by photocatalytic action.
- Hydrophilic layer 18 is made of porous SiO 2 . The film thickness is set to 15 nm, for example. The hydrophilic layer 18 provides antifogging properties.
- Reflectance adjusting layer 20 >> The reflectance adjustment layer 20 is made of a material having a lower refractive index than the photocatalyst layer 16, and for example, a mixture of Al 2 O 3 and Ta 2 O 5, a mixture of Al 2 O 3 and SnO 2 , Al 2 O 3.
- the reflectance adjustment layer 20 suppresses a decrease in reflectance caused by setting the thickness of the photocatalyst layer 16 to be thick (140 to 200 nm), and reduces a color shift due to a change in viewing angle.
- the function of reducing the decrease in reflectance and the color shift is mainly obtained with Al 2 O 3 .
- the reflectance adjusting layer 20 is composed of only Al 2 O 3 , the water resistance is insufficient. Therefore, the water resistance is improved by mixing Ta 2 O 5 , SnO 2 , ZrO 2 or the like.
- the Al 2 O 3 contained in the reflectance adjusting layer 20 is 50% or more and 95% or less (preferably 70% or more, 95 % Or less).
- Ta 2 O 5 contained in the reflectance adjustment layer 20 is set to 50% or less, 5% or more (preferably 30% or less, 5% or more).
- Al 2 O 3 contained in the reflectance adjustment layer 20 is set to 30% or more and 90% or less when the reflectance adjustment layer 20 is a mixture of Al 2 O 3 and SnO 2 .
- SnO 2 contained in the reflectance adjustment layer 20 is set to 70% or less and 10% or more.
- Al 2 O 3 contained in the reflectance adjustment layer 20 is set to 40% or more and 90% or less when the reflectance adjustment layer 20 is a mixture of Al 2 O 3 and ZrO 2 .
- ZrO 2 contained in the reflectance adjustment layer 20 is set to 60% or less and 10% or more.
- the maximum / minimum reflectance ratio decreases as the thickness of the reflectance adjustment layer 20 increases.
- the photocatalyst layer 16 must be thinner than that when the thickness is thin, The photocatalytic performance decreases.
- the film thickness of the photocatalyst layer 16 is first set to the minimum film thickness (140 to 200 nm) at which the photocatalytic performance near the saturation value can be obtained, and a predetermined reflection color (blue or green here) under this condition
- the film thickness of the reflectance adjustment layer 20 is set so that the maximum / minimum reflectance ratio is 2 or more and 4 or less.
- the film thickness of the reflectance adjustment layer 20 is set to 35 to 85 nm, characteristics satisfying the required conditions (reflectance necessary for an automobile mirror, photocatalytic performance near a saturation value, blue or green reflection color, maximum / Minimum reflectance ratio of 2 or more and 4 or less).
- the colored antifogging mirror 11 sequentially forms a reflective layer 14, a reflectance adjusting layer 20, a photocatalyst layer 16, and a hydrophilic layer 18 on the surface of a base material by a PVD method such as a vapor deposition method or a sputtering method, or other thin film forming steps. Can be manufactured.
- FIG. 4 shows an example of film formation conditions when the reflectance adjusting layer 20, the photocatalyst layer 16, and the hydrophilic layer 18 are formed by vapor deposition.
- Examples of the present invention and comparative examples will be described.
- Examples 1 to 8 and Comparative Examples 1 to 4 having specifications shown in FIG. 5 in which the film thickness of the photocatalyst layer 16 and the composition of the reflectance adjusting layer 20 are different are shown. It was manufactured (Comparative Example 4 has no reflectance adjustment layer 20), and various characteristics were measured.
- the thickness of the hydrophilic layer 18 was set to 15 nm.
- Spectral reflection spectra in the visible light region of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in FIGS. 6 to 13, respectively.
- FIG. 14 shows the amount of displacement, water resistance, and acid resistance.
- “Integral sphere reflectance” is a reflectance measured by an indirect measurement method using an integrating sphere of JIS standard D5705.
- Water resistance is the observation of the presence or absence of film peeling after each sample was immersed in tap water and boiled for 2 hours.
- “Acid resistance” is a method in which sulfuric acid having a concentration of 0.1 N was dropped onto the surface of each sample and left for 24 hours to observe the presence or absence of film peeling.
- Examples 1 to 4 a sufficiently high reflectance is obtained as an automobile mirror.
- the reason why the reflectance in Examples 1 to 4 is high is that the decrease in reflectance due to the formation of the photocatalyst layer 16 is suppressed by Al 2 O 3 constituting the reflectance adjustment layer 20. is there.
- Comparative Examples 2 and 3 having a large maximum / minimum reflectance ratio that is, a large ratio between a color tone that reflects strongly and a color tone that reflects weakly
- the maximum / minimum reflectance ratio is small, the color shift due to the change in the viewing angle is small.
- FIG. 15A shows the spectral reflection spectrum in the visible light region in Example 2 when the line-of-sight angle is 0 degree (viewed from the front in front of the mirror surface), 30 degrees, and 45 degrees.
- FIG. 15B shows the maximum reflectance value, the minimum reflectance value, and the maximum / minimum reflectance ratio in the visible light region according to the characteristics shown in FIG. 15A.
- FIG. 16A shows the spectral reflection spectrum in the visible light region when the viewing angle is 0 degree, 30 degrees, and 45 degrees for Example 3.
- FIG. 16A shows the spectral reflection spectrum in the visible light region when the viewing angle is 0 degree, 30 degrees, and 45 degrees for Example 3.
- FIG. 16B shows the maximum reflectance value, the minimum reflectance value, and the maximum / minimum reflectance ratio in the visible light region according to the characteristics shown in FIG. 16A.
- FIG. 17A similarly shows the spectral reflection spectrum in the visible light region when the line-of-sight angle is 0 degree, 30 degrees, and 45 degrees for Example 4.
- FIG. 17B shows the maximum reflectance value, the minimum reflectance value, and the maximum / minimum reflectance ratio in the visible light region according to the characteristics shown in FIG. 17A.
- FIG. 18A shows the spectral reflection spectrum in the visible light region when the line-of-sight angle is 0 degree, 30 degrees, and 45 degrees for Comparative Example 4.
- FIG. 18A shows the spectral reflection spectrum in the visible light region when the line-of-sight angle is 0 degree, 30 degrees, and 45 degrees for Comparative Example 4.
- FIG. 18B shows the maximum reflectance value, the minimum reflectance value, and the maximum / minimum reflectance ratio in the visible light region according to the characteristics shown in FIG. 18A.
- the maximum / minimum reflectance ratio is large
- the variation in the maximum / minimum reflectance ratio due to the change in the line-of-sight angle is large, so that the color tone greatly varies as the line-of-sight angle varies from 0 degrees.
- the blue color when the reflected color is 0 degree changes to a reddish color, or the color becomes lighter.
- FIG. 19 shows a spectral reflection spectrum in the visible light region of the conventional colored anti-fog mirror 10 (film thickness of the photocatalyst layer 16 is 75 nm) of FIG.
- the film thickness of the photocatalyst layer 16 is 75 nm, only a single maximum value is generated in the visible light range, and no minimum value is generated. Therefore, the change in reflectance due to the wavelength is gradual, and the color tone shift due to the change in the viewing angle. The problem does not occur. That is, the problem of color misregistration due to a change in line-of-sight angle occurs when the film thickness of the photocatalyst layer 16 where the change in reflectance due to the wavelength is steep is large.
- FIG. 20 shows a water-repellent car wash on the vehicle in which the colored anti-fog mirror 11 of Examples 1 to 4 and the conventional colored anti-fog mirror 10 of FIG. 2 (the film thickness of the photocatalyst layer 16 is 70 nm) are installed.
- the test result when the test which measures the water droplet contact angle on the mirror surface after repeating a mirror to UV and irradiating with ultraviolet rays was repeated is shown. According to FIG.
- the colored antifogging mirror 11 of Examples 1 to 4 is twice or more and nearly three times the number of repetitions until the water droplet contact angle suddenly increases as compared with the conventional colored antifogging mirror 10. It can be seen that the photocatalytic performance is dramatically improved as compared with the conventional colored anti-fog mirror 10.
- Example 5 A fifth embodiment of the colored antifogging mirror 11 according to the present invention shown in FIG. 1 will be described. This is one in which the reflected color is green.
- the configuration of each layer in Example 5 is as follows.
- ⁇ Reflection layer 14 >> Composition: Cr.
- ⁇ Reflectance adjusting layer 20 >> Composition: Al 2 O 3 (70% by volume) and Ta 2 O 5 (30% by volume) mixture, film thickness 70 nm.
- Photocatalyst layer 16 >> Composition: TiO 2 , film thickness: 165 nm.
- Hydrophilic layer 18 >> Composition: porous SiO 2 , film thickness: 15 nm.
- a sixth embodiment of the colored anti-fog mirror 11 according to the present invention shown in FIG. 1 will be described. This also has a green reflection color.
- the configuration of each layer in Example 6 is as follows.
- ⁇ Reflection layer 14 >> Composition: Cr.
- ⁇ Reflectance adjusting layer 20 >> Composition: Al 2 O 3 (70% by volume) and Ta 2 O 5 (30% by volume) mixture, film thickness 35 nm.
- Photocatalyst layer 16 >> Composition: TiO 2 , film thickness: 200 nm.
- Hydrophilic layer 18 >> Composition: porous SiO 2 , film thickness: 15 nm.
- Example 7 of the colored anti-fog mirror 11 according to the present invention shown in FIG. 1 will be described. This also has a green reflection color.
- the configuration of each layer in Example 7 is as follows.
- ⁇ Reflection layer 14 >> Composition: Cr.
- ⁇ Reflectance adjusting layer 20 >> Composition: Al 2 O 3 (50% by volume) and SnO 2 (50% by volume) mixture, film thickness 67 nm.
- ⁇ Photocatalyst layer 16 >> Composition: TiO 2 , film thickness: 165 nm.
- Hydrophilic layer 18 >> Composition: porous SiO 2 , film thickness: 15 nm.
- Example 8 An embodiment 8 of the colored anti-fog mirror 11 according to the present invention shown in FIG. 1 will be described. This also has a green reflection color.
- the configuration of each layer in Example 8 is as follows.
- ⁇ Reflection layer 14 >> Composition: Cr.
- ⁇ Reflectance adjusting layer 20 >> Composition: Al 2 O 3 (60% by volume) and ZrO 2 (40% by volume) mixture, film thickness 60 nm.
- Photocatalyst layer 16 >> Composition: TiO 2 , film thickness: 170 nm.
- Hydrophilic layer 18 >> Composition: porous SiO 2 , film thickness: 15 nm.
- 11 colored anti-fog mirror, 12 ... substrate (base material), 14 ... reflective layer, 16 ... photocatalyst layer, 18 ... hydrophilic layer, 20 ... reflectance adjustment layer
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Abstract
Description
《基材12》
基材12はソーダガラス等のガラス基板等で構成される。
《反射層14》
反射層14はCr等の金属で構成される。
《光触媒層16》
光触媒層16はTiO2で構成される。従来実用化されていた図2の有色防曇鏡10は反射色を青色系にするためにTiO2光触媒層16の膜厚を75nm程度に設定していた。これに対し、図1の有色防曇鏡11は反射色を青色系(または緑色系)にするために、光触媒層16の膜厚を140~200nmの厚い膜厚に設定する。光触媒層16は親水層18の表面に付着した有機物汚れを光触媒作用で分解して除去することにより、親水層18の防曇性を維持する。
《親水層18》
親水層18は多孔質SiO2で構成される。膜厚は例えば15nmに設定される。親水層18により防曇性が得られる。
《反射率調整層20》
反射率調整層20は光触媒層16よりも屈折率が低い材料で構成されるもので、例えばAl2O3とTa2O5の混合物、Al2O3とSnO2の混合物、Al2O3とZrO2の混合物等で構成される。反射率調整層20は光触媒層16の膜厚を厚く(140~200nm)設定したことに伴う反射率の低下を抑制するとともに、視線角度の変化による色調ズレを軽減する。反射率の低下および色調ズレを軽減する機能は主にAl2O3で得られる。但し反射率調整層20をAl2O3のみで構成すると、耐水性が不十分であるので、Ta2O5、SnO2、ZrO2等を混合することにより、耐水性を向上させる。反射率調整層20に含まれるAl2O3は、反射率調整層20がAl2O3とTa2O5の混合物の場合は、50%以上、95%以下(好ましくは70%以上、95%以下)に設定する。このとき反射率調整層20に含まれるTa2O5は50%以下、5%以上(好ましくは30%以下、5%以上)に設定する。また反射率調整層20に含まれるAl2O3は、反射率調整層20がAl2O3とSnO2の混合物の場合は、30%以上、90%以下に設定する。このとき反射率調整層20に含まれるSnO2は70%以下、10%以上に設定する。また反射率調整層20に含まれるAl2O3は、反射率調整層20がAl2O3とZrO2の混合物の場合は、40%以上、90%以下に設定する。このとき反射率調整層20に含まれるZrO2は60%以下、10%以上に設定する。有色防曇鏡11は反射率調整層20の膜厚が厚くなるほど極大/極小反射率比が小さくなる。しかし、反射率調整層20の膜厚を厚くした場合に、該膜厚が薄い場合と同様の反射色を得るためには、該薄い場合に比べて光触媒層16を薄くしなければならず、光触媒性能が低下する。ここで、光触媒層16の膜厚と光触媒性能の関係は図3のようになる。すなわち、膜厚が薄いときは膜厚の増加に従い光触媒性能も増加するが、膜厚が所定以上になると光触媒性能は飽和する。そこで、先に光触媒層16の膜厚を、飽和値付近の光触媒性能が得られる最低膜厚(140~200nm)に設定し、この条件下で所定の反射色(ここでは青色系または緑色系)が得られかつ極大/極小反射率比が2以上、4以下となるように反射率調整層20の膜厚を設定する。反射率調整層20の膜厚を35~85nmに設定すると、要求される条件を満たす特性(自動車用ミラーとして必要な反射率、飽和値付近の光触媒性能、青色系または緑色系の反射色、極大/極小反射率比が2以上、4以下)が得られる。
(a)実施例1~4および比較例1~4は反射率極大値における波長がほぼ等しく、反射色はいずれも青色系である。
(b)比較例4の積分球反射率はJIS規格D5705で規定された自動車用ミラーの反射率の下限値35%に近い値であり(40%以上の積分球反射率が自動車用ミラーとして適切である)、十分とは言えない。比較例4の反射率が低いのは、光触媒層16の膜厚を厚く形成したことによるものである。これに対し、実施例1~4は自動車用ミラーとして十分に高い反射率が得られている。実施例1~4の反射率が高いのは、光触媒層16の膜厚を厚く形成したことによる反射率の低下が、反射率調整層20を構成するAl2O3によって抑制されているためである。
(c)極大/極小反射率比が大きい(すなわち強く反射する色調と反射が弱い色調の比率が大きい)比較例2,3は視線角度の変化による色調ズレが大きい。これに対し、極大/極小反射率比が小さい実施例1~4は視線角度の変化による色調ズレが小さい。極大/極小反射率比が4以下であれば、色調ズレを実用上問題がない程度に軽減することができる。
(d)実施例1~4どうしを対比すると、実施例1よりも実施例2~4の方が積分球反射率が高く、極大/極小反射率比が小さい。したがって実施例1よりも実施例2~4の方がより高い反射率が得られ、かつ色調ズレをより軽減することができる。
(e)比較例2は耐水性が十分でない。これに対し、実施例1~4は耐水性、耐酸性とも十分である。
図16Aは同様に、実施例3について、視線角度が0度、30度、45度のときの可視光域での分光反射スペクトルを示す。図16Bは図16Aの特性による可視光域での反射率極大値、反射率極小値、極大/極小反射率比を示す。
図17Aは同様に、実施例4について、視線角度が0度、30度、45度のときの可視光域での分光反射スペクトルを示す。図17Bは図17Aの特性による可視光域での反射率極大値、反射率極小値、極大/極小反射率比を示す。
図18Aは同様に、比較例4について、視線角度が0度、30度、45度のときの可視光域での分光反射スペクトルを示す。図18Bは図18Aの特性による可視光域での反射率極大値、反射率極小値、極大/極小反射率比を示す。
図18Bによれば、極大/極小反射率比が大きい比較例4は視線角度の変化による極大/極小反射率比の変動が大きいので、視線角度が0度から変動するに従い色調が大きく変動し、反射色が0度のときの青色系から、赤みがかった色に変化したり、色が薄くなったりする。これに対し、図15B、図16B、図17Bによれば、極大/極小反射率比が小さい実施例2,3,4は、視線角度の変化による極大/極小反射率比の変動が小さいので、視線角度が0度から変動しても反射色の色調の変化は比較例4に比べて小さく抑える(すなわち色調ズレを軽減する)ことができる。因みに、図2の従来の有色防曇鏡10(光触媒層16の膜厚は75nm)の可視光域での分光反射スペクトルを図19に示す。光触媒層16の膜厚が75nmの場合は、可視光域に単一の極大値しか生じず、極小値は生じないので、波長による反射率の変化が緩やかであり、視線角度の変化による色調ズレの問題は起こらない。すなわち視線角度の変化による色調ズレの問題は波長による反射率の変化が急峻となる光触媒層16の膜厚が厚い場合に起こる。
《反射層14》組成:Cr。
《反射率調整層20》組成:Al2O3(70体積%)とTa2O5(30体積%)の混合物、膜厚70nm。
《光触媒層16》組成:TiO2、膜厚:165nm。
《親水層18》組成:多孔質SiO2、膜厚:15nm。
・積分球反射率:62%
・反射率極大値:78.3%(at 532nm)
・反射率極小値:25.1%(at 707nm)
・極大/極小反射率比:3.1
・反射色:緑色系
《反射層14》組成:Cr。
《反射率調整層20》組成:Al2O3(70体積%)とTa2O5(30体積%)の混合物、膜厚35nm。
《光触媒層16》組成:TiO2、膜厚:200nm。
《親水層18》組成:多孔質SiO2、膜厚:15nm。
・積分球反射率:63%
・反射率極大値:75.2%(at 556nm)
・反射率極小値:18.8%(at 734nm)
・極大/極小反射率比:4.0
・反射色:緑色系
《反射層14》組成:Cr。
《反射率調整層20》組成:Al2O3(50体積%)とSnO2(50体積%)の混合物、膜厚67nm。
《光触媒層16》組成:TiO2、膜厚:165nm。
《親水層18》組成:多孔質SiO2、膜厚:15nm。
・積分球反射率:64%
・反射率極大値:78.4%(at 530nm)
・反射率極小値:24.1%(at 715nm)
・極大/極小反射率比:3.2
・反射色:緑色系
《反射層14》組成:Cr。
《反射率調整層20》組成:Al2O3(60体積%)とZrO2(40体積%)の混合物、膜厚60nm。
《光触媒層16》組成:TiO2、膜厚:170nm。
《親水層18》組成:多孔質SiO2、膜厚:15nm。
・積分球反射率:65%
・反射率極大値:78.8%(at 530nm)
・反射率極小値:23.4%(at 716nm)
・極大/極小反射率比:3.4
・反射色:緑色系
Claims (16)
- 基材の表面に反射層、反射率調整層、光触媒層、親水層を順次積層した構造を有し、
前記光触媒層が実質的にTiO2で構成され、該光触媒層の膜厚が140~200nmであり、
前記親水層が実質的に多孔質SiO2で構成され、もって、
可視光域での反射率の極大値が波長430~560nmに存在し、反射色が青色系または緑色系を呈し、可視光域の反射率の極大値と極小値の比が2以上、4以下である有色防曇鏡。 - 前記反射率調整層が実質的にAl2O3とTa2O5の混合物で構成され、該反射率調整層に含まれるAl2O3の体積百分率が50%以上、95%以下である請求項1に記載の有色防曇鏡。
- 前記反射率調整層が実質的にAl2O3とSnO2の混合物で構成され、該反射率調整層に含まれるAl2O3の体積百分率が30%以上、90%以下である請求項1に記載の有色防曇鏡。
- 前記反射率調整層が実質的にAl2O3とZrO2の混合物で構成され、該反射率調整層に含まれるAl2O3の体積百分率が40%以上、90%以下である請求項1に記載の有色防曇鏡。
- 前記反射率調整層の膜厚が35~85nmである請求項1に記載の有色防曇鏡。
- 前記反射率調整層の膜厚が35~85nmである請求項2に記載の有色防曇鏡。
- 前記反射率調整層の膜厚が35~85nmである請求項3に記載の有色防曇鏡。
- 前記反射率調整層の膜厚が35~85nmである請求項4に記載の有色防曇鏡。
- 前記光触媒層の膜厚が165±20nmである請求項1に記載の有色防曇鏡。
- 前記光触媒層の膜厚が165±20nmである請求項2に記載の有色防曇鏡。
- 前記光触媒層の膜厚が165±20nmである請求項3に記載の有色防曇鏡。
- 前記光触媒層の膜厚が165±20nmである請求項4に記載の有色防曇鏡。
- 前記光触媒層の膜厚が150nmより大である請求項1に記載の有色防曇鏡。
- 前記光触媒層の膜厚が150nmより大である請求項2に記載の有色防曇鏡。
- 前記光触媒層の膜厚が150nmより大である請求項3に記載の有色防曇鏡。
- 前記光触媒層の膜厚が150nmより大である請求項4に記載の有色防曇鏡。
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