JP2001039220A - Hydrophilic mirror and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To fit a hydrophilic mirror onto a vehicle outside mirror to ensure proper visibility for a vehicle rearward worsened due to a rain drop or a blur, by fixing a mirror glass for displaying hydrophilic effect on a vehicle outside mirror surface, simply and at a low cost. SOLUTION: In an after-fitting hydrophilic outside mirror, a hydrophilically treated layer 2 and an aluminum or chrome evaporation layer 3 are filmed on the surface and the back surface of an outside mirror respectively, moreover a dispersion-preventive film 4 and a fitting double-side tape 5 are constituted on the layer 3, and light is reflected to the layer 3. In these cases, the outside mirror can be detachably fitted by a specific sheet, or magical tacking or sucking method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a hydrophilic mirror and a method for producing the same.

[0002]

2. Description of the Related Art A conventional mirror, particularly an outside mirror for a vehicle, is obtained by cutting a glass base material to a predetermined size, performing a process of forming a curved surface, and depositing or sputtering a reflective coat (aluminum or chrome) on the back surface of the glass. Had been manufactured. Further, the colored hydrophilic mirror exhibiting the hydrophilicity has not been commercialized.

[0003]

However, the outside mirror manufactured by such a conventional method does not have a hydrophilic effect, so that raindrops are hardly seen on the outside mirror surface in rainy weather, and there is a large temperature difference. In some cases, there are problems such as fogging of the outside mirror surface,
Install a small wiper on the outside mirror, incorporate an ultrasonic oscillator in the outside mirror body, vibrate the outside mirror when necessary to scatter raindrops, install a heater on the back of the outside mirror, Heating the outside mirror with the Joule heat of the heater and removing the fogging caused a high initial cost and could only be solved with a so-called genuine outside mirror. In addition, the ultrasonic type cannot be used for a long time because of the life of the oscillator and the electrical specifications of the vehicle, and it is necessary to frequently turn on and off the power switch during driving of the vehicle. The heater type has a poor response and has a technical problem that the outside mirror does not warm up immediately after the power switch is turned on. The present invention has been made to solve such a conventional problem, and a first object of the present invention is to provide a hydrophilic mirror (outside mirror) which has been subjected to a hydrophilic treatment. A second object of the present invention is to provide a method for producing a hydrophilic mirror (outside mirror) which has been subjected to a hydrophilic treatment. A third object of the present invention is to provide a hydrophilic mirror (outside mirror) which has been subjected to a hydrophilic treatment and can be easily mounted on a genuine outside mirror. A fourth object of the present invention is to colorize a hydrophilic mirror which is the object of the first to third objects.

[0004]

Means for Solving the Problems A first invention for solving the above-mentioned problems is a retrofit hydrophilic mirror for a vehicle, in which a mirror glass exhibiting a hydrophilic effect is fixed on an outside mirror surface for a vehicle. It is.

[0005] A second invention is the retrofit hydrophilic mirror for vehicles according to the first invention, wherein the fixing means uses a double-sided tape.

In a third aspect, the expression of the hydrophilic effect is as follows:
The retrofit hydrophilic mirror for a vehicle according to the first or second invention, which is provided by a photoexcitation effect of a photocatalyst. Here, as the photocatalyst, anatase type titanium oxide, rutile type titanium oxide, zinc oxide, strontium titanate, tin oxide, bismuth trioxide, tungsten trioxide, ferric oxide and the like can be suitably used. Reflective coatings include chrome, aluminum,
Silver etc. can be used. In the case of using the vapor deposition method, both the electron beam vapor deposition method and the heat vapor deposition method can be used. The mirrors for vehicles can be used, for example, as door mirrors for automobiles, fender mirrors, back mirrors for motorcycles and motorcycles, and the like.

In a fourth aspect, the expression of the hydrophilic effect is as follows:
The retrofit hydrophilic mirror for vehicles according to the first invention or the second invention, which is made of an alkali metal silicate-based material.

In a fifth aspect, the expression of the hydrophilic effect is as follows:
The post-installation hydrophilic mirror for a vehicle according to the first or second invention, wherein the photo-excitation action of the photocatalyst and the alkali metal silicate-based material are used.

A sixth invention is the retrofit hydrophilic mirror for a vehicle according to any one of the first to fifth inventions, wherein the retrofit hydrophilic mirror for a vehicle is colored.

According to a seventh aspect of the present invention, the mirror glass comprises a first glass.
The post-installation hydrophilic mirror for vehicles according to the sixth invention, comprising: a glass, a colored layer laminated on the first glass, and a second glass laminated on the colored layer. is there.

An eighth invention is a hydrophilic mirror provided with a coloring layer between a mirror and glass.

Further, the outside mirror according to the present invention may be attached to a housing in advance, or may be attached later to the surface of the outside mirror which has been attached in advance. Further, for example, the retrofit outside mirror may be detachable.

A ninth invention is directed to a first step of preparing a glass, a second step of applying a coating composition for hydrophilic treatment on the glass, and a third step of heat-treating the glass after application. This is a method for manufacturing a hydrophilic mirror, comprising: a step; and a fourth step of cutting, curving, and depositing / sputtering a reflective coat on the glass after the heat treatment.

In the step of performing a hydrophilic treatment on the surface of the glass plate in this production method, the composition is applied to the surface of the glass plate, and then subjected to a heat treatment to form a hydrophilic film. As the method for applying the composition, methods such as spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge coating can be suitably used. According to a preferred embodiment of the present invention, application by a spray coating method, a spin coating method, or a dip coating method is preferred. At this time, the surface applied to the glass plate is a surface (top surface) that is not in contact with the molten metal (tin) when passing through a tin bath process in a generally known float plate glass manufacturing process.
It is preferable to apply it. The top surface is free from impurities such as tin and iron mixed into the glass in the tin bath process, and can improve the film forming property at the time of applying the composition.

In the process of vapor deposition or sputtering of the reflective coat, a masking treatment is applied to the hydrophilic treated surface, so that the metal such as chromium, aluminum, and silver forming the reflective coat goes around the hydrophilic treated surface and hinders the performance. Can be prevented.

According to a tenth aspect of the present invention, there is provided a first step of preparing glass, a second step of cutting, curving, and depositing / sputtering a reflective coat on the glass; This is a method for producing a hydrophilic mirror, comprising: a third step of applying a coating composition for treatment; and a fourth step of heat-treating the glass after application.

In this manufacturing method, in the step of vapor deposition or sputtering of the reflective coat, the surface (the surface opposite to the reflective coat surface) is subjected to a masking treatment so that chromium, which forms the reflective coat on the surface, It is possible to prevent metal such as aluminum and silver from wrapping around. Further, it is preferable that the reflection coat is formed on the under surface (the surface in contact with the molten metal) during the glass production. As a result, the influence of impurities on the treated surface can be minimized during the hydrophilic treatment in the next step described later, and the film forming property of the composition can be improved.

In the step of performing a hydrophilic treatment on the mirror surface,
The composition is applied to the surface of a glass plate, and then heat-treated to form a hydrophilic film. As a method for applying the composition, a spray coating method and a spin coating method can be suitably used. According to a preferred embodiment of the present invention, application by a spray coating method is preferred.

According to an eleventh aspect, a first step of preparing glass, a second step of applying a coating composition for hydrophilic treatment on glass, and a step of heating the glass after application and simultaneously applying the curved surface And a third step of attaching.

The twelfth invention comprises a first step of preparing a first curved glass, a second step of applying a coating composition for hydrophilic treatment on the first curved glass, The third step of heat-treating the first curved glass, the fourth step of preparing the second curved glass and the colored layer, and the coating composition for hydrophilic treatment of the first curved glass is not applied. A fifth step of placing a colored layer on the surface and placing a second curved glass on the colored layer.

A thirteenth invention is the manufacturing method according to the twelfth invention, wherein the colored layer is selected from the group consisting of a colored resin, a colored film, and a colored adhesive.

In the step of forming a colored layer in this manufacturing method, it is effective to use a colored resin (modified EVA or PVB colored), a colored film (weathered PET colored) and a colored adhesive. Available to

In the step of performing the hydrophilic treatment on the surface of the glass plate in this production method, the composition is applied to the surface of the glass plate, and thereafter, the composition is subjected to a heat treatment to form a hydrophilic film. As the method for applying the composition, methods such as spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge coating can be suitably used. According to a preferred embodiment of the present invention, application by a spray coating method, a spin coating method, or a dip coating method is preferred. At this time, the surface applied to the glass plate is a surface (top surface) that is not in contact with the molten metal (tin) when passing through a tin bath process in a generally known float plate glass manufacturing process.
It is preferable to apply it. The top surface is free from impurities such as tin and iron mixed into the glass in the tin bath process, and can improve the film forming property at the time of applying the composition.

In order to industrially bond two sheets of curvature glass, chromium, aluminum,
No masking treatment is required to prevent a metal such as silver from wrapping around the hydrophilic treatment surface and hindering the hydrophilic treatment surface.

A fourteenth invention is the method for producing a hydrophilic mirror according to any one of the ninth to thirteenth inventions, wherein the coating composition for hydrophilic treatment contains photocatalyst particles.

The step of forming the photocatalyst-containing film on the outside mirror surface or the transparent substrate surface can be realized by various methods. One method is, for example, to prepare an amorphous titanium oxide precursor (organic titanium compound such as alkoxide, chelate or acetate of titanium, or inorganic titanium compound such as titanium tetrachloride or titanium sulfate). After being applied to the substrate, the precursor of amorphous titanium oxide is heated from room temperature to 200 ° C.
First, an amorphous titanium oxide thin film is formed by subjecting it to hydrolysis and dehydration-condensation polymerization at the above temperature. Next, the amorphous titanium oxide is changed into a crystalline titanium oxide by heating to a temperature higher than the crystallization temperature of the titanium oxide and lower than the softening point of the substrate. In another method, after forming an amorphous titanium oxide film by a vapor deposition method, the amorphous titanium oxide is heated to a temperature equal to or higher than the crystallization temperature of titanium oxide and equal to or lower than the softening point of the substrate to crystallize the amorphous titanium oxide. Phase change to crystalline titanium oxide. In another method, after applying the crystalline titanium oxide sol to the substrate, the crystalline titanium oxide is sintered and heated to a temperature lower than the softening point of the substrate to form the photocatalyst-containing film.

In this case, a binder may be added in addition to the crystalline titanium oxide for curing, and the curing can be performed at a temperature lower than the sintering temperature of the titanium oxide.

Further, in order to improve the hydrophilicity of maintaining darkness in a dark place, a compound containing silicon such as silica or silicone can be added in addition to titanium oxide or a titanium oxide precursor. In this case, it is more preferable that the silicon-containing compound also functions as the binder.

A fifteenth invention is directed to the method for producing a hydrophilic mirror according to any one of the ninth to fourteenth inventions, wherein the coating composition for hydrophilic treatment comprises an alkali metal silicate-based material. It is.

Preferred examples of the alkali metal silicate include alkali silicates represented by the general formula Me ₂ O.nSiO ₂ (where Me represents an alkali metal) (for example, water glass, potassium silicate, lithium silicate, Sodium silicate, and silica). In the present invention, the solution containing an alkali metal silicate is Fr, Cs, R
It comprises at least one metal selected from the group consisting of b, K, Na, and Li.

According to a preferred embodiment of the present invention, the alkali metal silicic acid-containing solution preferably contains a second component, and specific examples of the second component include Al, Ti, Si,
Zr, Zn, Ce, Sn, Sb, Sr, Fe, Cr,
P, B, Co, Mn, Cu, Ag, Pt, Au, V, T
and a metal selected from a and Bi and their metal compounds. Specific examples of these compounds include SiO ₂ , SiO ₃ , Si (OH), Al (O
H) ₃ , TiCl ₄ , Ti (OC ₃ H ₇ ) _{4 and the} like. By adding these second components, a function suitable for the purpose can be provided. For example, hydrophilicity is preferably Al ₂ O ₃ , TiO _2, or the like having a high heat of wetting with water. In addition, Ce having ultraviolet light self-deactivation is preferable for ultraviolet absorption,
If antibacterial properties are required, oxides of Cu and Ag are preferable.
Alkali metal oxides are highly effective in preventing stains such as oil stains and are thus preferable. Addition of P, B, etc. is preferable because the durability of the multifunctional material can be improved.

When a photocatalyst is used as the second component, the hydrophilicity due to photoexcitation of the photocatalyst can be used in addition to the hydrophilicity due to the alkali metal silicate-based material.

According to a preferred embodiment of the present invention, the concentration of the alkali metal silicate in the alkali metal silicate-containing solution is:
The solid content is preferably 0.001% to 35% by weight, more preferably 0.001% to 20% by weight. By being in the above range, a surface having good performance and good strength can be obtained. Further, a multifunctional material having a uniform and smooth surface and good gloss can be obtained.

Further, the alkali metal silicate-containing solution is
Rapid heating can generate a large amount of non-crosslinked oxygen on the surface of the multifunctional material. Here, non-crosslinked oxygen has the following meaning. Most solutions containing alkali metal silicates are MO
H (where M represents a metal element, specifically M is Si,
Ti, Al, Zr, Sn, Ta, Bi, etc.) are cross-linked by rapid heating and polymerized by forming MOM bonds, optionally with the second component Sticks to the surface. At this time, some M-OH exists without forming an MOM bond while being incorporated into the molecule of the formed polymer. Further, a part of the M-OH is ionically bonded to an ionic species (for example, sodium or the like) present in the alkali metal silicate-containing solution, and is reversibly M-OH + (here, M-OH). And X represents a cation such as a sodium ion). further,
According to the findings obtained by the present inventors, under the rapid heating conditions described below, the MOM bond can also be dissociated into the MOH bond by contact with water molecules in the air. Was observed. These M-OH and MOX + are referred to as non-crosslinkable oxygen in the present invention. This non-crosslinkable oxygen is extremely compatible with water molecules, and even captures water molecules in the air on the substrate surface. Further, when water comes into contact with the substrate surface, the non-crosslinked oxygen is more likely to bond with water molecules than the molecules that were present on the substrate surface prior to water, and therefore is present on the substrate surface first. The water molecules and the water molecules are exchanged, whereby the molecules previously existing on the substrate surface are dropped.
Therefore, the presence of the non-crosslinkable oxygen on the surface of the substrate, combined with the hydrophilicity of the second component, causes the surface of the substrate to exhibit extremely high hydrophilicity. As a result of this hydrophilicity, there is obtained an advantage that, of course, lipophilic stains can be easily washed away with water, not to mention hydrophilic stains.

According to the most preferred embodiment of the present invention, the alkali metal silicate-containing solution basically comprises (1) an alkali metal silicate, (2) a second component, and (3) a solvent. Comprising. According to a further preferred embodiment, the alkali metal silicate-containing solution comprises a surfactant. The addition of the surfactant makes it possible to apply the alkali metal silicate-containing solution uniformly. Further, the outside mirror according to the present invention may be attached to the housing in advance, or may be attached later to the surface of the outside mirror that has been attached in advance. Further, for example, the retrofit outside mirror may be detachable.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below in detail based on embodiments.

[0037]

(Embodiment 1) A first embodiment will be described. FIG. 1 shows a configuration of a retrofit hydrophilic outside mirror to which the present invention is applied. As shown in the figure, a hydrophilic treatment layer is formed on the outside mirror surface, an aluminum or chrome deposited layer is formed on the back surface of the outside mirror, and a film to prevent scattering and a double-sided tape for attachment Have been. This light is reflected by the aluminum or chrome deposited layer when viewed from the viewing direction in the figure.

FIG. 2 is a structural view of a case where the hydrophilic outside mirror of the present invention is actually mounted on a genuine outside mirror of a vehicle, and FIG. 3 is an installation in a case where the genuine outside mirror is damaged and does not exist. Indicates the status. As shown in the figure, a spacer having the same thickness as the genuine outside mirror that has been broken and is no longer attached is first attached with a double-sided tape, and the hydrophilic outside mirror of the present invention is attached on this spacer with a predetermined double-sided tape. Since the spacer has the same thickness as the genuine outside mirror that is no longer damaged, there is an advantage that the relative position of the hydrophilic outside mirror after attachment is not affected by the presence or absence of the genuine outside mirror.

In these cases, the hydrophilic outside mirror of the present invention may be detachably mounted by a special sheet, a magic tack method or a suction cup method. FIG.
Is an example of attachment via a magical tack.

(Embodiment 2) A second embodiment will be described. FIG. 5 shows a manufacturing process of the hydrophilic outside mirror of the present invention. As shown in the drawing, for example, after cutting a sheet glass of a standard size of 940 mm × 830 mm into a predetermined mirror size, a mirror manufactured in a normal mirror manufacturing process (curved surface, aluminum or chrome is deposited), for example, cerium oxide or After cleaning by ultrasonic cleaning, the following coating composition is coated on the mirror surface by a spray coating method. Thereafter, it is fired at a low temperature of about 150 to 350 ° C.

This coating composition was made of potassium silicate (Snowtex K, manufactured by Nissan Chemical Co., Ltd.)
It was prepared by mixing 1 part by weight of a 3% aqueous solution of copper acetate with 100 parts by weight of an aqueous solution containing 10% by weight.

After that, a mirror scattering prevention film and a double-sided tape for attachment are attached to predetermined positions for products that have passed the inspection (reflectance, distortion rate, shape, dimensions, etc.) of the mirror, and the production is completed. In this way, in this embodiment, since the hydrophilic treatment is performed under the low-temperature baking conditions after the usual mirror manufacturing, the deposited layer is not damaged at the baking temperature.

(Embodiment 3) A third embodiment will be described. FIG. 6 shows a manufacturing process of the hydrophilic outside mirror of the present invention. As shown in the drawing, for example, a glass plate having a standard size of, for example, 940 mm × 830 mm is coated uniformly on a mirror with a coating composition described in Example 2 by a spin coating method after a cleaning step using, for example, cerium oxide or ultrasonic cleaning. Then, after firing at about 700 to 800 ° C., it is cut into a mirror shape. After that, it takes about 30 minutes in a tunnel kiln at about 700 ° C to make a curved surface (for example, mirror curvature of a domestic passenger car is 1400m).
I do.

Thereafter, masking is carried out using a simple peeling film or the like so as to prevent deposition of aluminum or chrome on the surface of the mirror which has been subjected to the hydrophilic treatment (the effect of masking is disclosed in JP-A-10-295507). Vapor deposition takes about 30 to 40 minutes, and for mirrors that have passed inspection (reflectance, distortion rate, shape, dimensions, etc.), finally attach the mirror's anti-scattering film and double-sided tape for attachment to the specified position. Production ends. In this manner, in this embodiment, since the hydrophilic treatment is performed in the state of the sheet glass, and then the normal mirror forming treatment is performed, it is easy to control the film formation of the hydrophilic layer.

(Embodiment 4) A fourth embodiment will be described. FIG. 7 shows a manufacturing process of the hydrophilic mirror of the present invention. As shown in the drawing, for example, a 940 mm x 830 mm standard size sheet glass is cut into a predetermined mirror size, and then, for example, the following coating composition is coated on the mirror surface by a spray coating method after a cleaning step using cerium oxide or ultrasonic cleaning. . Thereafter, firing at about 700 to 800 ° C. and simultaneously performing a step of forming a curved surface (for example, a curvature of a domestic passenger car of 1400 mm) are performed.

This coating composition was mixed with a lithium silicate boric acid mixture (trade name SLN5, manufactured by Nippon Chemical Co., Ltd.).
5) and an anatase-type titanium oxide photocatalyst sol (average particle size: 10 nm) were mixed and prepared so that the respective concentrations became 0.1% by weight aqueous solution.

Thereafter, masking is performed using a simple peeling film or the like so that deposition of aluminum, chrome or the like does not enter the surface of the mirror that has been subjected to the hydrophilic treatment (the masking effect is disclosed in JP-A-10-295507). Vapor deposition takes about 30 to 40 minutes, and for mirrors that have passed inspection (reflectance, distortion rate, shape, dimensions, etc.), finally attach the mirror's anti-scattering film and double-sided tape for attachment to the specified position. Production ends. In this way, in this embodiment, since the baking process of the hydrophilic treatment and the normal mirror surface imposing process are performed at the same time, the cost of the product can be reduced by shortening the manufacturing process.

(Embodiment 5) A fifth embodiment will be described. After masking the back surfaces of a plurality of 25 cm square (1.9 mm thick) glass sheets with a resin, the glass sheets were immersed in a polymer solution of tetraalkoxysilane having a solid content of 5% (NSI500, manufactured by Nippon Soda), and 24 cm / The surface of the glass sheet was coated with a polymer of tetraalkoxysilane by a dip coating method of pulling up in minutes. Next, the coated glass sheet is immersed in an organic titanium compound solution (NTD-90, manufactured by Nippon Soda) having a solid concentration of 1.6%, and further dipped in at a rate of 24 cm / min. The layer surface was coated with an organotitanium compound; Thereafter, the masking resin on the back surface was peeled off. Then, the plate glass is heated at 550 ° C.
For 1 hour. It is considered that the polymer layer of tetraalkoxysilane is converted into an amorphous silica layer by hydrolysis and polycondensation through the steps so far. Further, the organic titanium compound was hydrolyzed, polycondensed, changed into amorphous titanium oxide, and then crystallized to form an anatase type titanium oxide.

Next, from the above-mentioned glass sheet, a long diameter of 15 cm,
Cut two pieces of oval glass with a short diameter of 10 cm, chamfer,
After washing with a brush and drying, the sample was heated to 650 ° C. and bent so that the surface on which the titanium oxide layer was formed became a convex surface to obtain a # 1 sample.

A mirror was prepared by performing the following six treatments on each of a plurality of # 1 samples. Treatment 1: After ultrasonic cleaning with an alkaline cleaning liquid for 15 minutes and distilled water for 30 minutes,
While masking the surface on which the titanium oxide layer was formed so that chromium did not adhere to the surface, chromium was fixed to the back surface of the # 1 sample by a sputtering method to obtain a # 2 mirror sample. Treatment 2: After ultrasonic cleaning with an alkaline cleaning solution for 15 minutes and distilled water for 30 minutes, chromium is fixed to the back surface of the # 1 sample by a sputtering method without masking the surface on which the titanium oxide layer is formed, and a # 3 mirror sample is prepared. Obtained.
Treatment 3: After performing brush cleaning for about 5 minutes, chromium is fixed to the back surface of the # 1 sample by sputtering while masking the surface on which the titanium oxide layer is formed so that chromium does not adhere to this surface, and the # 4 mirror sample is removed. Obtained. Treatment 4: After performing brush cleaning for about 5 minutes, chrome was fixed on the back surface of the # 1 sample by a sputtering method without masking the surface on which the titanium oxide layer was formed, to obtain a # 5 mirror sample. Treatment 5: Without cleaning, chromium was fixed to the back surface of the # 1 sample by sputtering while masking the surface on which the titanium oxide layer was formed so that chromium did not adhere to this surface, to obtain a # 6 mirror sample. Treatment 6: Chromium was fixed on the back surface of the # 1 sample by a sputtering method without washing and without masking the surface on which the titanium oxide layer was formed, to obtain a # 7 mirror sample.

For mirror samples # 2 to # 7, oleic acid was first applied to the surface on which the titanium oxide layer was formed, and then washed with a detergent.
Drying at <RTIgt; C </ RTI> allowed the surface to be deliberately rendered hydrophobic. Thereafter, the surface of the titanium oxide layer was irradiated with a BLB lamp having an ultraviolet illuminance of 0.1 to 0.2 mW / cm ² , and a change with time in the contact angle with water was examined. Table 1 shows the results.

[0052]

[Table 1]

According to Table 1, in the step of forming a chromium layer on the back surface, the surface of the photocatalyst-containing film was masked to prevent chromium from adhering to the photocatalyst-containing film.
For the # 6 sample, # 3, # 5,
It can be seen that the hydrophilicity is faster and the hydrophilicity retention is stable as compared with the # 7 sample. In addition, as a result of observation, it was also found that there was little local variation in hydrophilic performance.

From the above results, in the step of forming the chromium layer on the back surface, the surface of the photocatalyst-containing film is masked in order to prevent chromium from adhering to the photocatalyst-containing film. In this case, it is concluded that the recovery of the hydrophilicity of the surface of the photocatalyst-containing film is fast and the hydrophilicity retention is stable. Thereby, it is considered that the visibility in rainy weather is also stably exhibited.

(Embodiment 6) A sixth embodiment will be described. In the manufacturing process described in Example 2, the following coating composition is coated on the mirror surface. The coating composition was made of potassium silicate (manufactured by Nippon Chemical Industry Co., Ltd. 1
K potassium silicate) and titania sol (TN manufactured by Ishihara Sangyo Co., Ltd.)
P-06) was prepared by mixing after calcination so as to be 70% by weight and 30% by weight in terms of titania and potassium silicate, respectively.

The obtained coating composition was coated on a mirror surface by a spray coating method, and the surface temperature was adjusted to 350 ° C. in an electric furnace tunnel kiln.
Bake for 0 minutes. Then, it was left in a room and cooled to room temperature to produce an outside mirror of Example 1.

Next, an initialization test was performed according to the following procedure.
The coating surface was irradiated with a BLB lamp having an ultraviolet irradiance of 0.5 mW / cm ² for 1.5 hours, and then the contact angle with water was measured with a contact angle meter. The contact angle was 5 degrees or less, showing extremely excellent hydrophilicity.

Next, a photocatalytic evaluation experiment was performed on the above sample in the following procedure. After oleic acid was applied to the coated surface, it was washed off with a detergent and dried at 50 ° C. to intentionally make the surface hydrophobic. Then BL of ultraviolet illuminance 0.5mW / cm ²
The coating surface was irradiated with a B lamp to examine the time change of the contact angle with water. The initial contact angle is 28.1 °,
The contact angle after decomposition was 1.9 °, indicating excellent decomposition activity.

Further, a washing and abrasion resistance test was conducted according to the following procedure. Attach a sponge to the slider of the sliding tester,
With a load of 20 g / cm ² , 10
The slide was performed 00 times. After that, the surface was visually observed, but no abnormal appearance such as damage or peeling of the film was observed. After that, the coating surface was irradiated with a 0.5 mW / cm ² BLB lamp, and the time change of the contact angle with water was examined. The initial contact angle was 27.5 °, and the contact angle after the recovery of hydrophilicity was 6.5 °, indicating an extremely high hydrophilicity recovery.

(Embodiment 7) A seventh embodiment will be described. In the manufacturing process described in Example 2, the following coating composition is coated on the mirror surface. Coating composition, lithium silicate boric acid mixture (Nippon Kagaku Kogyo Co., Ltd. SLN73) and titania sol (Ishihara Sangyo Co., Ltd. TNP-06), after firing, titania, 70% by weight, 30% by weight in terms of silica Prepared by mixing as described above.

The obtained coating composition was coated on the mirror surface by a spray coating method, and the surface temperature was adjusted to 350 ° C. in an electric furnace tunnel kiln.
Bake for 0 minutes. Then, it was left in a room and cooled to room temperature to produce an outside mirror of Example 1.

In an initialization test similar to that in Example 6, the contact angle was 5 ° or less, and extremely high hydrophilicity was exhibited. Also,
In the photocatalytic test, the contact angle after decomposition was 2.8 °, showing extremely high decomposition activity. In the washing and abrasion resistance test, the contact angle after the recovery of the hydrophilicity was 6.8 °, showing extremely high hydrophilicity recovery.

(Eighth Embodiment) An eighth embodiment will be described. FIG. 8 shows the configuration of a colored retrofit hydrophilic outside mirror to which the present invention is applied. As shown in the figure, the outer curved glass A having a hydrophilic treatment layer formed on the surface and the inner curved glass B having chromium or aluminum deposited or sputtered on the surface or the back are colored resins (preferably polyvinyl butyral). It is a structure industrially bonded with a resin or PVB), and is further formed of a double-sided tape for attachment inside the structure. Because it has the same structure as laminated glass,
No external adhesive film is required to prevent scattering. This light is reflected by the aluminum or chrome deposited layer when viewed from the viewing direction in the figure.

(Embodiment 9) A ninth embodiment will be described. FIG. 9 shows a manufacturing process of the colored hydrophilic mirror of the present invention. As shown in the figure, for example, a 940 mm x 830 mm standard size sheet glass is cut into a predetermined mirror size, and then washed, for example, by cerium oxide or ultrasonic cleaning, and then the following coating composition is spray-coated on the glass surface. Coat. The softening point of the glass (680-700)
B) firing at the following temperature.

This coating composition was made of potassium silicate (Snowtex K, manufactured by Nissan Chemical Co., Ltd.)
It was prepared by mixing 1 part by weight of a 3% aqueous solution of copper acetate with 100 parts by weight of an aqueous solution containing 10% by weight.

Then, after the other mirror is industrially bonded with the colored resin, the double-sided adhesive tape is attached to a predetermined position, and the production is completed.

(Embodiment 10) A third embodiment will be described. FIG. 10 shows a manufacturing process of the colored hydrophilic mirror of the present invention. As shown in the figure, a glass plate having a standard size of, for example, 940 mm × 830 mm is uniformly coated on a glass with the coating composition described in Example 9 by a spin coating method after a cleaning step using, for example, cerium oxide or ultrasonic cleaning.
Then, after firing at about 700 to 800 ° C., it is cut into a mirror shape. Thereafter, the surface is curved (for example, mirror curvature R1400 of a domestic car) in a tunnel kiln of about 700 ° C. for about 30 minutes.

Then, after the other curved mirror is industrially joined with the colored resin, the double-sided adhesive tape is attached to a predetermined position, and the production is completed. In this way, in the present embodiment, the hydrophilic treatment is performed in the state of the sheet glass, and then the mirror forming treatment is performed, so that the formation of the hydrophilic layer can be easily controlled.

[0069]

According to the present invention, a mirror exhibiting hydrophilicity can be mounted on an outside mirror of a vehicle.
As in the prior art, it is possible to relatively easily and inexpensively secure the rear view of the vehicle due to raindrops and cloudiness. Further, according to the present invention, since the mirror exhibiting hydrophilicity can be freely attached to and detached from the outside mirror of the vehicle, it can be attached to and detached from a plurality of vehicles with one mirror. It can be easily achieved at low cost.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a configuration of a hydrophilic mirror according to one embodiment of the present invention.

FIG. 2 is a diagram showing an example of mounting on a genuine mirror;

FIG. 3 is a diagram showing an example of attachment when a spacer is interposed.

FIG. 4 is a diagram showing an example of mounting when a magical tack is used;

FIG. 5 is a manufacturing process diagram according to one embodiment of the present invention.

FIG. 6 is a manufacturing process diagram according to one embodiment of the present invention.

FIG. 7 is a manufacturing process diagram according to one embodiment of the present invention.

FIG. 8 is a diagram showing the structure of a colored post-attached hydrophilic mirror;

FIG. 9 is a manufacturing process diagram of a colored hydrophilic mirror.

FIG. 10 is a manufacturing process diagram of a colored hydrophilic mirror.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Glass substrate 2 ... Hydrophilic film 3 ... Aluminum or chrome vapor deposition layer 4 ... Shatterproof film 5 ... Double-sided adhesive tape 6 ... Peeling tape 7 ... Genuine mirror 8 ... Genuine mirror press cover 9 ... Hydrophilic mirror 10 ... Mirror drive Apparatus 11 Mirror casing 12 Spacer 13 Magical tack 14 Curved glass A 15 Hydrophilic film 16 Curved glass B 17 Aluminum or chrome deposited layer 18 Colored vinyl chloride butyral (PVB) 19 Double-sided tape for mounting 20 ... peeling tape

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) C09K 3/18 C09K 3/18 (72) Inventor Tetsuya Fukushima 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture No. 1 TOTO Co., Ltd. in the F-term (reference) 3D025 AA02 AC20 AD13 3D053 FF19 HH25 HH38 JJ11 JJ16 4G069 AA03 AA08 BA02B BA04A BA04B BA14A BA14B BA15A BA15B BA48A BB04A BB04B BB06A BB06B BC03A BC03B BC04A BC04B BC31A BC31B BD03A BD03B BD05A BD05B CD10 EA07 ED02 FA03 FB23 FB24 4H020 AA01 AB02 4J038 EA011 HA456 KA04 NA16 PC03

Claims (15)

[Claims] 1. A retrofit hydrophilic mirror for a vehicle, wherein a mirror glass exhibiting a hydrophilic effect is fixed on an outside mirror surface for a vehicle. 2. The retrofit hydrophilic mirror for vehicles according to claim 1, wherein said fixing means uses a double-sided tape. 3. The retrofit hydrophilic mirror for a vehicle according to claim 1, wherein the manifestation of the hydrophilic effect is caused by a photoexcitation effect of a photocatalyst. 4. The retrofit hydrophilic mirror for a vehicle according to claim 1, wherein said hydrophilic effect is expressed by an alkali metal silicate-based material. 5. The retrofit hydrophilic mirror for a vehicle according to claim 1, wherein the manifestation of the hydrophilic effect is caused by a photoexcitation effect of a photocatalyst and an alkali metal silicate-based material. 6. The retrofit hydrophilic mirror for a vehicle according to claim 1, wherein the retrofit hydrophilic mirror for a vehicle is colored. 7. The mirror glass comprises: a first glass; a colored layer laminated on the first glass; and a second glass laminated on the colored layer. Item 7. A retrofit hydrophilic mirror for vehicles according to Item 6. 8. A hydrophilic mirror having a coloring layer between a mirror and glass. 9. A first step of preparing a glass, a second step of applying a coating composition for hydrophilic treatment on the glass, a third step of heat-treating the glass after application, and heating. A fourth step of cutting, curving, and depositing / sputtering a reflective coat on the glass after the treatment. A method for producing a hydrophilic mirror, comprising: 10. A first step of preparing a glass; cutting and curving the glass;
A hydrophilic step comprising: a second step of performing a sputtering treatment; a third step of applying a coating composition for hydrophilic treatment on the treated glass; and a fourth step of heat-treating the applied glass. Manufacturing method. 11. A first step of preparing a glass, a second step of applying a coating composition for hydrophilic treatment on glass, and a third step of heating and simultaneously applying a curved surface treatment to the glass after application. And a method for producing a hydrophilic mirror comprising: 12. A first step of preparing a first curved glass, a second step of applying a coating composition for hydrophilic treatment on the first curved glass, and a first curved glass after the application. A third step of heat-treating, a fourth step of preparing a second curved glass and a colored layer, and a colored layer on the surface of the first curved glass on which the hydrophilic treatment coating composition has not been applied. And place the second on the colored layer.
And a fifth step of mounting the curved glass of the above. 13. The method according to claim 12, wherein said colored layer is selected from the group consisting of a colored resin, a colored film, and a colored adhesive. 14. The method for producing a hydrophilic mirror according to claim 9, wherein said coating composition for hydrophilic treatment contains photocatalyst particles. 15. The method for producing a hydrophilic mirror according to claim 9, wherein said coating composition for hydrophilic treatment comprises an alkali metal silicate-based material.