JPH09165232A - Non-iridescent transparent electroconductive film and glass having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a film and a glass with the film capable of being used in a single glass as the window material of a vehicle, having both functions as a protective film and a reflection reducing film, etc., non-iridescent, excellent in durability, being a transparent electroconductive film, having no heat feeling owing to its heat ray shielding property and enhancing an air conditioning effect. SOLUTION: In this non-iridescent transparent electroconductive film prepared by forming a transparent electroconductive film as a first layer from a base board side and an overcoat film as a second layer on a transparent base board surface, the overcoat film has a refractive index obtained as a square root of the refractive index of the transparent electroconductive film and the non- iridescent transparent electroconductive film has a thickness >=0.15 times and <=0.35 times wave length of a light having >=500nm and <=600nm wave length. A glass having the film is also claimed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an achromatic transparent conductive film and a glass with a film, which are used for a film-coated heat ray-shielding glass such as a window for a building or a window for a vehicle. It is possible to block the light and improve the heating and cooling effect, and it is friendly to people and the environment, and has a relatively high visible light transmittance and
A glass thin film with an achromatic transparent conductive film having a toral (colorless or colorless unevenness) tone, for example, a glass having a protective film, a reflection reduction film, an antistatic coating film with antistatic property or low emissivity. The present invention relates to an achromatic transparent conductive film and a glass with the film, which enables multi-functionalization.

[0002]

2. Description of the Related Art In recent years, heat ray shielding glass has been constructed for the purpose of shielding solar radiation energy flowing into a room or a vehicle through a building window glass, a vehicle window glass or the like to reduce a temperature rise in the room or the vehicle and a cooling load. It is used as window glass for vehicles and window glass for vehicles.

In addition, recently, glass having various functions in addition to high heat ray shielding performance can be provided by various film constitutions, and a reflection color tone due to film thickness variation and interference in a large area glass can be provided. Since it is necessary to be gentle to people and the environment, it is desired to prevent color unevenness from being perceived by the eyes, and various proposals have been made.

For example, Japanese Examined Patent Publication (Kokoku) No. 63-39535 discloses an achromatic glass structure, which is composed of at least one transparent glass sheet and an infrared-reflecting substance installed on the sheet. In the structure including the first inorganic coating layer, wherein the infrared reflective material is a transparent semiconductor and is a type of material exhibiting a chromatic color in daylight illumination, the second coating layer is a glass sheet. Located between the first cover layer and for reflecting and refracting light such that the second cover layer substantially reduces the visible color of the first cover layer in daylight illumination. Means for forming with the body of the second cover layer at least 2.
A second coating layer is defined as the square root of the product of the index of refraction of the glass sheet and the index of refraction of the first coating layer to provide a means of substantially reducing the chromatic color by providing two interfaces. Having a refractive index, and the second coating layer is 500n
It is disclosed to have a quarter wavelength thickness of light having a wavelength in m 2 of vacuum.

Among them, for example, the second coating layer is 1.7-
It has a refractive index of 1.8 and a thickness of 64-80 nm.
The coating layer has a refractive index of 2, and the glass sheet has a refractive index of 1.5. For example, the second coating layer is a metal oxide, a metal nitride or a mixture thereof, and Al ₂ O ₃ , SiO ₂ , Zn
O, MgO, SnO ₂ , In ₂ O ₃ , GeO ₂ , Ga ₂ O ₃ and Si ₃ N ₄ is selected from the group, and the thickness of the semiconductor layer, for example, stannic oxide, is less than 0.4 μ, It is described that the total film thickness of the first coating layer and the second coating layer is 0.1 to 1 μm.

[0006] For example, Japanese Patent Publication No. 3-72586 discloses that
A non-glazing glass structure is described, comprising: (a) a transparent substrate, (b) an infrared reflective transparent semiconductor coating having a thickness of 0.1 to 1.0 micron, and (c) a substrate. A non-irractive, transparent sheet structure of the type including an intermediate layer member that suppresses irritation between the infrared-reflective transparent semiconductor coating and the infrared-reflective transparent semiconductor coating. Two components, a first intermediate layer component and a second intermediate layer component, between the coating and the transparent substrate, that is, (1) close to the substrate and of the formula d ₁
= (1/720) cos ^-1 [(r ₁ ² + r ₂ ² -r ₃ ² ) / 2r ₁ r ₂ ] [where r ₁ = (n ₁ -n
_g ) / (n ₁ + n _g ), r ₂ = (n ₁ -n ₂ / (n ₁ + n ₂ ), r ₃ = (n _c -n ₂ / (n
_c + n ₂ ) n _g = Refractive index of substrate, n ₁ = Refractive index of first intermediate layer component, n ₂ =
The refractive index of the second intermediate layer component, n _c = the refractive index of the infrared reflective transparent semiconductor coating)], and the first intermediate layer component having an optical thickness d ₁ given by The equation d ₂ = (1/720) cos ^-1 [(r ₂ ² +
r ₃ ² −r ₁ ² ) / 2r ₂ r ₃ ], the second intermediate layer component having an optical thickness d ₂ . [The refractive index (n ₁ ) of the first intermediate layer component is higher than the refractive index (n ₂ ) of the second intermediate layer component, n ₁ > n ₂ and d ₁ and d ₂ are 500 nanometers. Given in units of design wavelength] is disclosed.

Further, for example, in Japanese Patent Laid-Open No. 3-164449,
A non-glare glass is described, and a high refractive index transparent thin film having a refractive index n of 1.8 or more and a thickness d of 0.15 μm or more is formed on a glass substrate, and n = n is provided between the high refractive index transparent thin film and the glass substrate. 1.65 ~ 1.8 transparent underlayer film has an optical film thickness nd = 0.1 ~ 0.18
It is an achromatic glass formed to a thickness of μm, and the transparent underlayer film is a composite oxide containing at least one of Zr, Ti, Ta, Hf, Mo, W, Nb, Sn, La and Cr and Si. It is disclosed that the film is mainly composed of a substance.

[0008] Among them, it is described that in the case of non-colored (colorless unevenness) glass, indium tin oxide, fluorine-doped tin oxide, zinc oxide and the like are used as the high refractive index transparent thin film.

Further, for example, in Japanese Patent Laid-Open No. 4-270136,
A method for making a film composed of aluminum and an oxide of tin or titanium, and a product thereof are described, wherein a non-hydrolyzable aluminum chelate and at least one organotin compound, or a titanium chelate and a titanium alcoholate are described. By thermally decomposing a solution consisting of, and on high temperature glass, Al ₂ O ₃ --SnO ₂ (for example, refractive index 1.66 to 1.
76) or Al ₂ O ₃ —TiO ₂ (eg 1.73 to 1.80 refractive index) films are disclosed between the glass support and the semiconducting metal oxide film (eg 100 to 800 nm thick). It is described that a window glass having a semiconductor film whose reflected light is achromatic can be obtained by using a film of Al ₂ O ₃ -SnO ₂ or Al ₂ O ₃ -TiO ₂ (for example, a thickness of 80 to 100 nm). There is.

Further, for example, in Japanese Patent Laid-Open No. 5-116992,
An anti-glare transparent body is described, in which a transparent thin film having a refractive index of 1.6 or more and a film thickness of 0.15 μm or more is formed on a transparent substrate,
An underlayer is formed at the interface between the transparent thin film and the transparent substrate to form an antiglare transparent body, and the underlayer is an absorptive film having an extinction coefficient k of not 0. Further, the antiglare transparent body comprises a transparent substrate on which a transparent thin film having a refractive index of 1.6 or more and a film thickness of 0.15 μm or more is formed, and an upper layer is formed on the transparent thin film. The upper layer has an extinction coefficient k of 0. Not an absorbent membrane. In addition, a transparent thin film with a refractive index of 1.6 or more and a film thickness of 0.15 μm or more is formed on the transparent substrate, an underlayer is formed at the interface between the transparent thin film and the transparent substrate, and an upper layer is formed on the transparent thin film. The extinction coefficient k of the transparent layer is 0 for the underlayer and the upper layer.
It is each disclosed to be a non-absorbent membrane.

Among them, for example, the refractive index ng of the transparent substrate is
1.4 to 1.6, and the "transparent thin film" is a film whose extinction coefficient k is a small value (k≈0) such that k can be ignored in optical calculation, and the refractive index nf is 1.6 to 2.3. Specific examples thereof include ITO, SnO ₂ : F, ZnO: Al, and ZnO. As the absorbent underlayer or upper layer, the film thickness is 10 to 500.
Å, a metal simple substance, a nitride, a carbide, or a composite thereof, preferably at least one metal simple substance selected from titanium, chromium, and zirconium, a nitride, a carbide, or a composite thereof, and The upper and lower layers are TiN, CrN, CrC, ZrN, and the underlying layer is TiN / C.
r, TiN / Ti / TiN, Cr / TiN, Cr / ZrN, etc. are mentioned as the upper layer.

Further, for example, in Japanese Patent Laid-Open No. 5-193994,
An anti-iridescent transparent inlaid glazing article having an anti-iridescent coating that is tolerant to deviations in the thickness and refractive index of the anti-iridescent and optically functional coating. Also, JP-A-5-193995 discloses a transparent iridescent coating having a gradient refractive index, which has an iridescent preventing layer that is tolerant to variations in the thickness and refractive index of the iridescent preventing layer and the optically functional layer. Inlaid glazing articles are each disclosed.

Further, for example, Japanese Patent Application Laid-Open No. 7-41337 discloses an anti-glare transparent body, which has a transparent conductive film on a transparent substrate and has a base film between the transparent substrate and the transparent conductive film. In the transparent body, a mixed layer composed of the constituent components of the transparent conductive film and the underlying film is interposed between the transparent conductive film and the underlying film, and the mixed layer is the underlying film between the underlying film and the transparent conductive film. It is disclosed that the refractive index gradually increases from the one closer to the transparent conductive film.

Further, for example, Japanese Patent Application Laid-Open No. 7-10607 describes a glass article having a colorless coating giving a low emissivity and a method for producing the same, and a colorless coating giving a low emissivity is disclosed. In a glass article having
a. a transparent substrate having a refractive index in the range of about 1.5 to 1.6,
b. a first transparent coating layer having a refractive index in the range of about 1.66 to 1.73 and a thickness in the range of about 400 to 600Å; c.
A second transparent coating layer having a refractive index in the range of 76 to 1.83 and a thickness in the range of about 350 to 550Å, and d.
Disclosed is a metal oxide coating layer having a refractive index of 1.86 and a thickness sufficient to reduce the emissivity of a coated substrate below the emissivity of an uncoated substrate. ing.

In addition, in order to obtain at least achromatic color, a coating of an oxide film such as SiO ₂ as a base layer is disclosed in Japanese Patent Publication No. 3-48145.
1-201046, JP-A-5-294672 and JP-A-5-294672
There is a 4-265253 publication.

[0016]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, the achromatic glass structure described in Japanese Patent Publication No. 63-39535 and the like, and any glass having an achromatic function described in each of the above publications The underlying layer is provided with a film for achromatic rendering, and even if the underlying layer is provided with a film for achromatic rendering, a functional film such as a conductive film or an infrared reflective film in the upper layer. It is not possible to impart various strengths and / or properties such as reflection reduction of the above, and therefore, in order to obtain achromaticity and these imparting functions, a functional film is used as an underlayer film for achromaticity and an upper layer for imparting functions. It was necessary to sandwich with the membrane, which resulted in a cost increase.

[0017]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art. A transparent conductive film is provided on a transparent substrate, and then a specific refractive index relating to the refractive index of the transparent conductive film is provided. Rate, and by covering and laminating an overcoat film having a thickness of a wavelength equal to or less than a specified multiple of light of a specific wavelength, by providing an achromatic transparent conductive film and glass with the film, Not only the overcoat film, which is a non-lighting film, exhibits its original function, but it is also possible to simultaneously provide, for example, a protective film function, a reflection reduction function, an antistatic function, and the like. It has excellent barrier properties, and can exhibit its characteristics in a well-balanced manner without being related to the refractive index of a transparent substrate, and it is possible to obtain a more excellent achromatic transparent conductive film and glass with the film, which is a single plate and various types. Something with functional performance No various also be sufficiently used in automotive window material, and provides a useful non-glow transparent conductive film and the film-coated glass to be optimal for recent needs.

That is, the present invention provides a transparent substrate surface,
In an achromatic transparent conductive film formed by depositing a transparent conductive film as the first layer and then an overcoat film as the second layer from the substrate surface side, the overcoat film is transparent. Has a refractive index obtained as the square root of the value of the refractive index of the conductive film, and
0.15 times or more of light having a wavelength of 500 nm or more and 600 nm or less 0.
An achromatic transparent conductive film having a wavelength thickness of 35 times or less.

Further, the overcoat film is an oxide thin film, a halide thin film, a sulfide thin film or a mixed thin film of two or more kinds selected from these, and the film thickness is 45.
The achromatic transparent conductive film described above, which is made of a transparent film having a wavelength of not less than 160 nm and not more than 160 nm and a refractive index of not less than 1.3 and not more than 1.7.

The transparent conductive film has a film thickness of 80 nm or more.
The achromatic transparent conductive film described above, which is 800 nm or less and has a refractive index of 1.6 or more and 2.8 or less. Further, the transparent conductive film has an average visible light transmittance of 70% or more at a wavelength of 0.38 μm to 0.70 μm and an infrared reflectance of 60% or more at a wavelength of 10 μm. Transparent conductive film.

Furthermore, the present invention provides a glass plate with an achromatic transparent conductive film, characterized in that the achromatic transparent conductive film is formed on the surface of a glass substrate.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, a transparent conductive film is formed on the transparent substrate surface from the substrate surface side as the first layer, and then the second conductive film.
In an achromatic transparent conductive film formed by forming an overcoat film as a layer, the overcoat film has a refractive index obtained as a square root of the value of the refractive index of the transparent conductive film. Have,
And an achromatic transparent conductive film having a thickness of 0.15 times or more and 0.35 times or less of light having a wavelength of 500 nm or more and 600 nm or less,
Obtain as follows.

First, the transparent substrate is an inorganic transparent substrate such as soda lime type glass, borosilicate type glass, non-alkali type glass, and quartz. Particularly, a transparent colorless or transparent substrate manufactured by the so-called float method. Colored plate glass, for example, green glass, bronze glass, gray glass, blue glass, or various transparent conductive films, such as glass coated with a heat ray shielding film or a Low-E film, is used.

Next, as a transparent conductive film which is the first layer
For example, ITO (In_TwoO_Three+ SnO_TwoDope film, NESA (SnO_Two,
SnO_Two+ Sb_TwoO_Five, SnO_Two+ F_Two) Membrane, various fluorine compound membranes, AZO
(Zinc to Al_TwoO_ThreeDope) film, other ZnInO_4-xMembrane, MgInO
_4-xMembrane, MgGaO_4-xMembrane, SbInO_4-xMembrane, ZrGa_TwoO_FourMembrane, Cd_TwoSnO_Four
 Membrane, CdGa_TwoO_Four Membrane, CdSb_TwoO_FourMembrane, Zn_FourInSbO₈System film, SbZn_Two
O _FourSystem film, Sb_TwoZn₇O₁₂System film, ZnSb_TwoO₆System film, ZnO-Ga system
Membrane, MgIn_TwoO_FourMembrane, ZnO-In_TwoO_ThreeExamples include F-based membranes and the like.
Films that exhibit functionality such as line-shielding films and Low-E films
Which is any of the transparent conductive films.

Above all, for example, the film thickness of the transparent conductive film is about
80 nm or more and 800 nm or less, and the refractive index of the transparent conductive film
Is preferably 1.6 or more and 2.8 or less, and more
Average visible in the wavelength range of 0.38μm to 0.70μm
The light transmittance is about 70% or more, and the wavelength is about 10 μm.
Average infrared reflectance of about 60% or more, and about 70%
It is more preferable that the degree is not less than,
Sheet resistance is 1 x 10 ^FourΩ / mouth ~ 1 x 10^FiveΩ / mouth
The transparent conductive film is most suitable as the transparent conductive film, and
The most achromatic effect can be achieved while utilizing the functions.
It will be

Subsequently, the overcoat film as the second layer has a refractive index obtained as a square root of the value of the refractive index of the transparent conductive film and has a wavelength of 500 nm or more and 600 nm or less. It has a wavelength thickness of 0.15 times or more and 0.35 times or less.

That is, as the overcoat film, x = √n; x is the refractive index of the overcoat film, and n is the refractive index of the transparent conductive film (for example, n = 1.6). ~ 2.8), over
The film thickness of the coat film = [(2n-1) λ × (0.15 to 0.35)] / x, preferably the film thickness = [(2n-1) λ × 0.25] / x, where λ is the design The wavelength (500 nm to 600 nm) is preferably about 550 nm, and n: 1, 2, 3, ... (The smaller the value, the more preferable).

As shown in FIG. 2, the glass 1 with an achromatic transparent conductive film of the present invention has a transparent conductive film 3 formed on a glass 2 which is a substrate, and then on the surface of the transparent conductive film 3. As the overcoat film 4 which is an optical film, a substrate glass and a thin film having a refractive index lower than that of the transparent conductive film are laminated by coating, and the transparent conductive film 3 and the overcoat film with respect to the incident light Y are laminated. 4 reflected light b (reflected light on the transparent conductive film surface) from the interface,
The surface reflection light a at the interface between the coat film 4 and air (reflected light at the surface of the overcoat film) is shifted in phase to cancel out the reflected light. Show things,
It is possible to simplify and explain the phenomenon of expressing achromaticity in the glass 1 with an achromatic transparent conductive film of the present invention. That is, due to the phase shift of the reflected lights a and b (the wavelength of b is shifted due to the longer optical path length), the lights of the reflected lights a and b cancel each other out to become achromatic.

Specific overcoat films include an oxide thin film, a halide thin film, a sulfide thin film, or a thin film of a mixture of two or more selected from these, and the like, and the film thickness is 45 nm or more and 160 nm or more. It is a film made of a transparent film having a refractive index of 1.3 or more and 1.7 or less. Overcoat film is 45
When the thickness is less than nm, the phase difference between the reflected light on the overcoat surface and the reflected light on the lower surface (the upper surface of the transparent conductive film) is small and it is impossible to cancel each other due to interference (reflected light a and b Since there is no difference in the optical path length and the phase shift is small and it cannot be canceled, it is impossible to achromatize, and when it exceeds 160 nm, the width of the wavelengths that cancel each other due to interference is narrow (the part where the reflected light becomes flat is narrow). Both sides stand up), large vibration occurs in the visible light wavelength and it does not become achromatic.

Further, when the refractive index is less than 1.3, there is no practically durable film having high stable physical strength (for example, MgF ₂ film: n = 1.39), and the non-irradiated film has an upper surface. The intensity of the reflected light is weaker than the intensity of the reflected light on the lower surface, and it is impossible to cancel each other out.
Then, b will remain). When the refractive index exceeds 1.7, the intensity of the reflected light on the upper surface of the achromatic film becomes too strong as compared with the intensity of the reflected light on the lower surface, and it is impossible to cancel each other out (achromatic light a >> b). ).

Not only can it be used as a single plate, but it can also be used with various types of laminated glass or laminated glass, glass with a shade band, bilayer glass, tempered glass, etc. It goes without saying that it can be used as various existing flat glass products as a glass plate. The plate thickness is, for example, about
It is preferably about 0.5 mm or more and about 10 mm or less, and more preferably about 2.0 mm or more and about 5.0 mm or less, a colorless or colored glass.

As described above, the achromatic transparent conductive film of the present invention and the glass with the film are obtained by forming a transparent conductive film on a transparent substrate,
Then, by coating and laminating an overcoat film having a specific refractive index relating to the refractive index of the transparent conductive film, and a thickness of a wavelength not more than a specified multiple of light of a specific wavelength,
By using the non-glare transparent conductive film and the glass with the film, the overcoat film which is the non-glazing film not only exhibits its original function but also has, for example, a protective film function or a reflection reducing function. It is also possible to have such properties as at the same time, and it has excellent heat ray-shielding properties, and exhibits its properties in a well-balanced manner without being related to the refractive index of the transparent substrate, and a more excellent achromatic transparent conductive film and glass with the film. Can be obtained, and can be sufficiently used for various automobile window materials including those that are single-paneled and have various functional performances.
The layer structure has high abrasion resistance and high durability, and has an effect of making visible light transmittance, visible light reflectance, solar radiation transmittance, and stimulation stimulus of reflection in a well-balanced manner.

Moreover, the solar radiation transmittance can be improved and the optical characteristics such as the visible light reflectance can be appropriately balanced, and the excellent heat ray shielding performance can be obtained, which reduces the feeling of heat and heat and enhances the effect of cooling and heating. And a useful achromatic transparent conductive film and a glass with the film which can be used as a single plate and can be secured in a comfortable environment inside and outside the vehicle, and which is optimal for the recent needs. It is provided.

[0034]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

Example 1 A float glass plate (FL5) having a size of about 300 mm × 300 mm and a thickness of about 3 mm was sequentially washed with a neutral detergent, water rinse, isopropyl alcohol, and dried to obtain a glass plate for film formation. .

First, monobutyltrichlorotin [(C ₄ H ₉ )]
SnCl ₃ ] about 100 g and ammonium hydrogen fluoride 3 g
Was dissolved in a mixed solvent of 550 g of dichloromethane, about 300 g of ethanol, and about 50 g of pure water, and the solution made up to about 1000 g was fluorine-doped tin oxide film (hereinafter referred to as NESA film).
Was used as a coating liquid A.

Subsequently, the coating solution A for the NESA film is pre-approx.
On the float glass plate that has been heated to about 550 ° C,
A two-fluid spray gun was used to spray at a coating amount of about 250 g / min for about 10 seconds to obtain a fluorine-doped tin oxide film having a film thickness of about 280 nm and a refractive index of about 2.0.

Next, monomethyltriethoxysilane [C
About 120 g of H ₃ Si (OC ₂ H ₅ ) ₃ ] and about 880 g of ethanol were added to make a total of about 1000 g, which was designated as coating liquid B for overcoat (for non-lighting).

Then, the coating solution B for the overcoat is applied onto the fluorine-doped tin oxide film of the glass plate with the fluorine-doped tin oxide film by the same method as described above. After spraying for about 7 seconds, the film thickness is about 98 nm and the refractive index is about 1.
The SiO ₂ film of 41 was obtained as an overcoat film.

The obtained fluorine-doped tin oxide film and SiO ₂
The glass with a transparent conductive film having two layers of films was evaluated by the following measurements. (Measurement and evaluation method) Optical characteristics: Visible light transmittance (380 nm to 780 nm), visible light reflectance (380 nm to 780 nm), solar radiation transmittance (340 nm to 1800 nm), emissivity ε, etc. (Hitachi Ltd.) and JIS Z8722, JIS R 3106 were used to determine the respective optical characteristics.

An emissivity ε of about 0.3 or less was regarded as acceptable. Mechanical properties: (Traverse test) (Abrasion resistance) Broad cloth # 40, load 100g / cm ² , stroke: 100mm, change amount of haze (fog condition) value after 5000 times (HH%).

* In all cases, the ΔH% was 4% or less, and the result was passed. Chemical characteristics: (Acid resistance) (Chemical resistance) After immersing the test piece in 0.1N H ₂ SO ₄ solution at room temperature for about 24 hours, the appearance is visually judged.

(Alkali resistance) After the test piece was immersed in a 0.1N NaOH solution at room temperature for about 24 hours, the appearance was visually judged.

* In both cases, the appearance was visually inspected and no change was observed, and the result was regarded as acceptable. Electrical characteristics: Measured by Mitsubishi Yuka's surface resistance meter (Loresta-AP).

(Surface resistance value) (Ω / mouth). Regarding the film thickness of each thin film, an uncoated portion was formed at the time of coating each thin film, and the step difference was measured with a surface roughness meter (DEKTAK30-30, manufactured by SLOAN).

As a result, the emissivity ε was 0.25, the visible light transmittance was 70% or more, the visible light reflectance was 7.0%, the solar radiation transmittance was about 65% or less, and the stimulation purity was 3.2%. %Met.

In particular, as shown in FIG. 1, which shows the state of reflectance (%) in the wavelength range of 380 to 780 (nm), it becomes achromatic and has sufficiently excellent optical characteristics such as heat ray shielding property and sufficiently stable. Shows acid resistance, cold heat resistance and excellent wear resistance,
It shows each physical property in a well-balanced manner, has excellent habitability, is friendly to the driver, passengers, and the environment, and maintains safety.
It was the intended glass with an achromatic transparent conductive film, which was intended by the present invention and can be sufficiently applied to automobile window glasses.

It should be noted that alkali resistance, weather resistance (eg, about 1000 hours with a Sunshine weather meter: no abnormality in appearance), humidity resistance (eg, about 30 ° C., about 95% RH for about 15 days:
When there were no abnormalities in appearance) and other various characteristics were evaluated, all passed.

Regarding the float glass (thickness of about 3 mm), the emissivity ε was 0.90, the visible light reflectance was 8.2%, and the stimulus purity was about 1.7%. The visible light reflectance is shown in FIG. Like

Comparative Example 1 Using the coating solution A for tin oxide film of Example 1, a film was formed in the same manner as in Example 1 to obtain a single layer film of only fluorine-doped tin oxide film.

The obtained glass with a single layer film containing only a fluorine-doped tin oxide film was evaluated by the same evaluation means as the measuring method shown in Example 1. As a result, the emissivity ε is 0.23, the visible light reflectance is 13.4%,
The stimulation purity was 27.1%.

Further, the reflectance (%) of visible light was as shown in FIG. 1, which was far from the desired glass with a non-transparent transparent conductive film aimed at by the present invention. Comparative Example 2 First, titanium tetraisopoxide [Ti (OC ₂ H ₅ ) ₄ ] 255 g
45 g of tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ] was dissolved in 700 g of ethanol, and this was used as a coating liquid C for the underlayer.

Subsequently, the coating liquid C for the underlayer was applied to the above-mentioned float glass plate which had been heated to about 200 ° C. in advance by a two-fluid spray gun at an application amount of about 250 g / min. After spraying for about 2 seconds, and then baking at about 500 ℃ for about 30 minutes, TiO ₂ -SiO ₂ with a film thickness of about 80 nm and a refractive index of about 1.74.
A film was obtained.

Then, the coating solution A for the fluorine-doped tin oxide film of Example 1 was used to form a film on the surface of the TiO ₂ —SiO ₂ film in the same manner as in Example 1, and the film was formed. A fluorine-doped tin oxide film having the same film thickness and refractive index as in Example 1 was coated and laminated.

The obtained glass with a two-layer film of TiO ₂ —SiO ₂ film and fluorine-doped tin oxide film was evaluated in Example 1.
The same evaluation method was performed by the measuring method shown in. As a result, the emissivity ε was 0.23, the visible light reflectance was 14.2%, and the stimulus purity was 7.6%.

The reflectance (%) of the visible light was as shown in FIG. 1, which was not the desired glass with a non-transparent transparent conductive film aimed at by the present invention. Comparative Example 3 First, using the coating solution A for fluorine-doped tin oxide film of Example 1, a film was formed in the same manner as in Example 1, and fluorine having the same film thickness and refractive index as in Example 1 was formed. A doped tin oxide film was obtained as the first layer.

Next, titanium tetrapropoxide [Ti (iO
C ₃ H _{7) 4]} 270 g and tetraethoxysilane [Si (OC
30 g of ₂ H ₅ ) ₄ ] was dissolved in 700 g of ethanol, and this was used as coating liquid D for the upper layer.

Subsequently, the foil previously heated to about 200 ° C.
Fluorine doping of float glass plate with fluorine doped tin oxide film
On the surface of the tin oxide film, two fluids of the coating liquid D for the upper layer are formed.
With a spray gun, the coating amount is about 250 g / min for about 2 seconds.
Spray for about 30 minutes and then bake at about 500 ° C for about 30 minutes.
As a result, TiO with a film thickness of about 76 nm and a refractive index of about 1.8_Two-SiO _Two
The membrane was overlaid.

The obtained fluorine-doped tin oxide film and TiO ₂ -SiO
For a two-layer film-coated glass of ₂ film, carrying out the Evaluation Example 1
The same evaluation method was performed by the measuring method shown in. As a result, the emissivity ε was 0.23, the visible light reflectance was 13.6%, and the stimulus purity was 25.4%.

Further, the visible light reflectance (%) was as shown in FIG. 1, which was not the desired glass with a non-transparent transparent conductive film aimed at by the present invention. Comparative Example 4 A film was formed in the same manner as in Example 1 except that the same coating liquids A and B as in Example 1 were used and only the coating liquid B was sprayed for a longer period of about 20 seconds. Over-co
A SiO ₂ film having a film thickness of about 320 nm and a refractive index of 1.41 was obtained as a coating film.

The glass having a two-layer film formed of the fluorine-doped tin oxide film and the SiO ₂ film was evaluated by the same evaluation means as the measuring method shown in Example 1. as a result,
Emissivity ε is 0.30 and visible light reflectance is 4.6.
%, And the stimulation purity was 74.7%.

Further, the visible light reflectance (%) was as shown in FIG. 1, which was not the desired glass with an achromatic transparent conductive film that the present invention aimed at.

[0063]

As described above, according to the present invention,
The light having a refractive index obtained as the square root of the refractive index value of the transparent conductive film and having a wavelength of 500 nm or more and 600 nm or less.
A two-layer laminated film using an overcoat film specified to have a thickness of 15 times or more and 0.35 times or less, and a glass on which the film is formed are achromatic. It exhibits functionality such as conductivity, heat ray blocking property, reflection reduction property and antistatic property, has excellent abrasion resistance, corrosion resistance and durability, enhances protection, and has well balanced optical properties. The present invention efficiently provides an achromatic transparent conductive film and a glass with the film, which can be used not only as a double glazing or the like but also as a single plate glass and is particularly useful as a window glass for an automobile as well as a window glass for an automobile.

[Brief description of the drawings]

FIG. 1 shows wavelengths of 380 to 78 for Example 1 relating to the glass with a non-glare transparent conductive film of the present invention, Comparative Examples 1 to 4 relating to glass with a non-glare transparent conductive film, and Float glass.
It is explanatory drawing which shows the state of reflectance (%) between 0 (nm).

FIG. 2 shows incident light Y, reflected light a (reflected light on the surface of the overcoat film) and reflected light b (reflection on the surface of the transparent conductive film) in the glass with an achromatic transparent conductive film of the present invention. It is explanatory drawing explaining the phenomenon which achromaticity develops by (light).

[Explanation of reference numerals] 1 glass with a non-transparent transparent conductive film 2 glass 3 transparent conductive film 4 overcoat film

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location H01B 1/00 9459-5L H01B 1/00 Z 5/14 5/14 A

Claims (5)

[Claims] 1. An achromatic transparent conductive film formed by depositing a transparent conductive film as a first layer and then an overcoat film as a second layer on the transparent substrate surface from the substrate surface side, The overcoat film has a refractive index obtained as a square root of the value of the refractive index of the transparent conductive film, and has a thickness of 0.15 times or more and 0.35 times or less of light having a wavelength of 500 nm or more and 600 nm or less. An achromatic transparent conductive film having: 2. The oxide film is an oxide thin film,
A halide thin film, sulfide thin film, or a mixture thin film of two or more selected from these, with a film thickness of 45 nm or more 16
The achromatic transparent conductive film according to claim 1, comprising a transparent film having a thickness of 0 nm or less and a refractive index of 1.3 or more and 1.7 or less. 3. The transparent conductive film has a film thickness of 80 nm or more and 800 n or more.
The achromatic transparent conductive film according to claim 1 or 2, wherein the transparent conductive film has a refractive index of 1.6 or more and 2.8 or less and m or less. 4. The transparent conductive film has a wavelength of 0.38 μm to 0.70.
The achromatic transparent conductive film according to claim 1, wherein the average visible light transmittance at 70 μm is 70% or more, and the infrared reflectance at a wavelength of 10 μm is 60% or more. 5. A glass plate with an achromatic transparent conductive film, wherein the achromatic transparent conductive film according to claim 1 is formed on the surface of a glass substrate.