JPH08138446A - Glass plate with transparent conductive film and transparent touch panel using it - Google Patents

Abstract

PURPOSE: To provide a glass plate with a transparent conductive film and a transparent touch panel using it by forming thin films, which respectively contain SiO2 , SnO2 , TiO2 , SiO2 , SiO2 as principal constituents and are provided with specific thickness individually, on a glass plate. CONSTITUTION: In a glass plate with a transparent conductive film, the first layer 3, which comprises a thin film containing SiO2 as a principal constituent and serves as an under coating layer, the second layer 4 comprising a thin film which contains SnO2 as a principal constituent, the third layer 5 comprising a thin film which contains TiO2 as a principal constituent, and the fourth layer 6 comprising a thin film which contains SiO2 as a principal constituent are sequently formed on a glass plate 2 in order. Thickness from the glass plate 2 to the second layer 4 is set to 30-120nm, thickness of the third layer 5 is set to 10-110nm, thickness of the fourth layer 6 is set to 30-120nm, and thickness of the fifth layer 7 is set to 20-30nm. In this way, the glass plate provided with a transparent conductive film, in which visible radiation transmittance is high while wavelength dependency of the transmittance is low, is formed.

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a glass plate with a transparent conductive film and a transparent touch panel used for various input devices.

[Prior art]

A transparent touch panel is used as an input means for various devices such as a calculator, a remote controller, a telephone, a copy machine, an electronic notebook, a control device, a mobile terminal device, a game device, and an educational device. Conventionally, as a glass plate with a transparent conductive film and a transparent touch panel used for such an application, a first layer composed of a thin film containing SiO 2 as a main component, S, on a glass plate.
A glass plate with a transparent conductive film in which a second layer made of a transparent conductive film containing nO2 as a main component is sequentially laminated, and a glass plate with a transparent conductive film is used as a first electrode plate, and a transparent conductive film may be provided. A transparent touch panel is known in which a transparent transparent plate is used as a second electrode plate, and a first electrode plate and a second electrode plate are arranged to face each other with a predetermined gap.

By the way, a transparent conductive film is required to have a high visible light transmittance and a linearity of a resistance value. Here, the linearity of the resistance value indicates the degree of the proportional relationship between the resistance value and the distance between two points when an arbitrary point is selected with respect to a certain starting point. The resistance is measured, and the standard deviation is divided by the average value, which is evaluated as a percentage.

Further, a glass plate with a transparent conductive film and a transparent touch panel using the same are required to have higher visible light transmittance and higher linearity of resistance value as the performance of a mobile terminal used is improved. For example, regarding the visible light transmittance, the transmittance at a wavelength of 550 nm is 93
% Or more, and the linearity of the resistance value is required to be 5% or less.

[0005]

However, a first layer made of a thin film containing SiO2 as a main component and a second layer made of a transparent conductive film containing SnO2 as a main component are sequentially laminated on the above-mentioned conventional glass plate. In the formed glass plate with a transparent conductive film, the transmittance is determined by the optical constant of tin oxide (SnO2), and even if the film thickness is selected, the transmittance at a wavelength of 550 nm (hereinafter referred to as T550) is 89- The limit is 90%, and a high transmittance T550 = 93% or more cannot be obtained.

[0006] Therefore, the applicant of the present invention, first on the glass plate,
First layer composed of a thin film containing SiO2 as a main component, TiO2
There is proposed a glass plate with a transparent conductive film, in which a second layer containing Si as a main component and a third layer containing a transparent conductive film containing SnO 2 as a main component are sequentially laminated. According to this, T550 = 9
Although 2% is obtained, there are peaks and valleys in the spectral transmittance curve,
It has been insufficient in terms of obtaining a flat transmittance in the visible light region.

[0007]

In order to solve the above-mentioned problems, the glass plate with a transparent conductive film according to claim 1 is provided on the glass plate,
SnO2, a first layer composed of a thin film containing SiO2 as a main component
A second layer formed of a thin film containing TiO2 as a main component, a third layer formed of a thin film containing TiO2 as a main component, a fourth layer formed of a thin film containing SiO2 as a main component, and a fifth layer formed of a thin film containing SnO2 as a main component. Are sequentially laminated, and the thickness of the second layer is 30 to
120 nm, the thickness of the third layer is 10 to 110 nm, the thickness of the fourth layer is 30 to 80 nm, and the thickness of the fifth layer is 20 to 30 n.
m.

A transparent touch panel according to a second aspect is the first aspect.
The glass plate with a transparent conductive film according to claim 1 is used as a first electrode plate, and the flexible transparent plate provided with a transparent conductive film is used as a second electrode plate. The transparent conductive film of the electrode plate was arranged to face each other with a predetermined gap. Here, the two electrode plates are arranged so as to face each other with the transparent conductive films covered by the respective plates facing inside.

The present invention will be described below with reference to the accompanying drawings. FIG. 1 is a schematic configuration diagram of a glass plate with a transparent conductive film according to the present invention.

In this glass plate 1 with a transparent conductive film, a first layer 3 as an undercoat layer composed of a thin film containing SiO 2 as a main component is formed on a glass plate 2, and Sn is formed on the first layer 3.
The second layer 4 made of a thin film containing O2 as a main component is
On the layer 4, a third layer 5 composed of a thin film containing TiO 2 as a main component
On the third layer 5, a fourth layer 6 made of a thin film containing SiO 2 as a main component and a fifth layer 7 made of a thin film containing SnO 2 as a main component are sequentially laminated on the fourth layer 6. Become.

Here, the glass plate 2 is not limited to the transparent glass, as long as it has been conventionally used for the glass plate with the transparent conductive film, such as float glass.

A first thin film composed mainly of SiO2
The layer 3 is for preventing sodium or the like contained in the substrate from diffusing into the second layer 4 and the fifth layer 7 containing SnO2 as a main component and affecting the electrical characteristics thereof. Since the first layer 3 does not affect the optical characteristics, its thickness may be a thickness sufficient to function as an undercoat layer, and is preferably 10 to 50 nm, more preferably 20 to 30 nm. SiO2
As a method for forming a thin film containing as a main component, SiH4 (monosilane) and O2 (oxygen) are mixed in 400
It is preferable to apply an atmospheric pressure CVD method in which the reaction is performed at ˜600 ° C. It is also possible to mix a compound of P (phosphorus) or B (boron) in the raw material and use a thin film containing SiO 2 containing these elements as a main component.

When a non-alkali glass mainly composed of borosilicate glass is used as the glass plate 2, Si is used.
The first layer 3 composed of a thin film containing O2 as a main component can be omitted.

A second thin film composed mainly of SnO2
The layer 4 is provided to increase the transmittance of the glass plate with the transparent conductive film. From the viewpoint of productivity, the atmospheric pressure CVD method in which a tin compound containing chlorine and oxygen are reacted at 400 to 600 ° C. is suitable as a method for forming a thin film containing SnO 2 as a main component. As a tin compound containing chlorine,
Monobutyltin trichloride and tin tetrachloride (SnCl4)
Etc. are used.

The thickness of the second layer 4 composed of a thin film containing SnO2 as a main component is preferably 30 to 120 nm, more preferably 60 to 100 nm. Film thickness is 3
When the thickness is less than 0 nm, the transmittance in the long wavelength region decreases, and
When the thickness is thicker than 20 nm, the transmittance in the short wavelength region decreases. Further, it is desirable that the second layer 4 has a high sheet resistance so as not to affect the sheet resistance of the fifth layer 7 even when short-circuited with the fifth layer 7 due to the influence of a pinhole or the like. 10 kΩ / □ or more is preferable. SnO
The high resistance of the thin film mainly composed of
It can be performed by doping with a trivalent metal element such as 1) or indium (In).

A third thin film composed mainly of TiO2
The layer 5 is provided to increase the transmittance of the glass plate with the transparent conductive film. As a method for forming a thin film containing TiO 2 as a main component, a normal pressure CVD method in which a titanium compound and an oxidizing agent such as oxygen are reacted at 400 to 600 ° C. is suitable. Titanium compounds include titanium tetraisopropoxide (Ti (OCH (CH3) 2) 4) and titanium tetra-n-butoxide (Ti (OCH2CH2CH).
2CH3) 4) and other alkoxides, di-i-propoxy bis (acetylacetonato) titanium (Ti (OCH
(CH3) 2) 2 (OC (CH3) CHCOCH3)
2) and other β-diketone chelates and titanium tetrachloride (Ti
Cl4) can be used.

The thickness of the third layer 5 composed of a thin film containing TiO2 as a main component is preferably 10 to 110 nm, more preferably 20 to 90 nm. Film thickness 10
When the thickness is less than nm, the transmittance in the long wavelength region decreases,
When it is thicker than 0 nm, the transmittance in the short wavelength region is lowered.

Fourth thin film composed mainly of SiO2
The layer 6 is provided to increase the transmittance of the glass plate with the transparent conductive film, and is formed in the same manner as the first layer 3. The thickness of the fourth layer 6 is preferably 30 to 80 nm, more preferably 40 to 70 nm.
When the film thickness is thinner than 30 nm, the transmittance in the long wavelength region decreases, and when it is thicker than 80 nm, the transmittance in the short wavelength region decreases.

Fifth thin film mainly composed of SnO2
The layer 7 is provided to impart conductivity to the glass with a transparent conductive film according to the present invention. The fifth layer 7 is formed in the same manner as the second layer 4, but HF, CF3Br, CH3CHF2 are added to the source gas in order to adjust the conductivity.
A compound containing fluorine such as or a compound containing antimony such as antimony pentachloride may be mixed and fluorine or antimony may be added to the film.

The thickness of the fifth layer 7 is preferably 20 to 30 nm, more preferably 20 to 25 nm. When the film thickness is less than 20 nm, the linearity of the resistance value exceeds 5%, and when it is more than 30 nm, the transmittance decreases.

[0021]

In a glass plate with a transparent conductive film obtained by forming a thin film on the surface of a glass plate, a first layer as an undercoat layer made of a thin film containing SiO 2 as a main component is formed on the surface of the glass plate. 30-120 nm thickness on the layer
And a second layer formed of a thin film containing SnO2 as a main component,
TiO2 having a thickness of 10 to 110 nm on the second layer
A third layer composed of a thin film containing as a main component, a fourth layer composed of a thin film containing SiO2 as a main component having a thickness of 30 to 80 nm on the third layer, and a thickness of 20 to 20 on the fourth layer. Thirty
By sequentially stacking and forming a fifth layer made of a thin film of SnO2 having a wavelength of 0.5 nm, the transmittance at a wavelength of 550 nm is 93% or more, and the transmittance in the visible light region is 8%.
It becomes 7% or more, and the transmission spectrum of visible light becomes nearly flat.

According to the transparent touch panel of the present invention using the glass plate with the transparent conductive film, the visibility is improved and it is possible to support color display.

[0023]

EXAMPLE A glass plate 1 with a transparent conductive film of the present invention is described below.
A specific example of the transparent touch panel will be described. Example 1 A float glass having a size of 300 * 320 mm and a thickness of 1.1 mm and a transmittance of 92% at a wavelength of 550 nm was washed and dried to obtain a glass plate (substrate). This board is 4
The substrate was heated to 50 ° C., and a gas in which SiH 4, N 2, and O 2 was adjusted was supplied to the surface of the substrate to form a first layer having a thickness of 30 nm and containing SiO 2 as a main component. Then the substrate is 500
The mixture was heated to 0 ° C., and a gas having adjusted C4H9SnCl3 vapor, N2, O2, and water vapor was supplied to form a second layer containing SnO2 as a main component having a thickness of 80 nm on the film surface of the first layer. Then, a vapor of Ti [OCH (CH3) 2] 4, a gas adjusted with N2 and O2 is supplied to adjust the thickness to 2
A third layer containing 0 nm of TiO 2 as a main component was formed. Then, a thickness of 40 nm is formed on the third layer in the same manner as above.
The fourth layer containing SiO 2 as a main component was formed. Finally,
C4H9SnCl3 vapor, CH3CHF2, N2, O
2 and a regulated gas of water vapor were supplied to form a fifth layer containing SnO 2 as a main component and having a thickness of 30 nm on the surface of the fourth layer.

The glass plate with a transparent conductive film having a laminated structure thus obtained was gradually cooled to prepare a sample, and the visible light transmittance of this sample was measured by a spectrophotometer. This measurement result is shown by the solid line in FIG. As can be seen from the figure, the transmittance at a wavelength of 550 nm was 94%, and the minimum value of the transmittance in the visible light region was 90%.

Further, when the linearity was evaluated by measuring the sheet resistance at 10 points where a straight line passing through the center of the sample and parallel to the long side was divided into 11 equal parts, the linearity of the resistance value was 3%.
Met.

Next, a transparent touch panel using the above glass plate 1 with a transparent conductive film will be described with reference to FIG. As shown in FIG. 1A, the transparent touch panel 11 has a glass plate with a transparent conductive film as a first electrode plate 12, and a flexible transparent substrate 17 provided with a transparent conductive film 18.
Is used as the second electrode plate 13, and the first electrode plate 12 and the second electrode plate 13 are arranged to face each other with a predetermined gap, for example, about 100 μm, via a spacer 14 that is a gap forming member.

In this transparent touch panel, normally, the liquid crystal 2 is placed in a gap between two glass plates 22 and 23 having transparent conductive films which face each other.
4 is used as an input device in combination with a liquid crystal display panel 21. In the case of an input device in which the liquid crystal display panel 21 is arranged in parallel with the glass plate with the transparent conductive film which is the second electrode plate 12 as shown in FIG. 3B, the second electrode plate 1 facing the liquid crystal display panel 1
It is possible to improve the visibility by applying an antireflection treatment to the surface of the glass 2 which is the second substrate. It is also possible to insert a refractive index adjusting agent in the gap between the transparent touch panel 11 and the liquid crystal display panel 21 to improve the visibility. Further, as shown in FIG. 3C, the transparent conductive film 26 for driving the liquid crystal display panel is formed on the surface of the glass 2 of the second electrode plate 12, and the touch panel and the liquid crystal display panel are integrated to improve the visibility. Can be improved.

Example 2 A sample was obtained in the same manner as in Example 1 except that the thickness of the second layer was 90 nm and the thickness of the third layer was 10 nm. The transmittance of this sample at a wavelength of 550 nm is 93%,
The minimum value of the transmittance in the visible light region was 89%, and the linearity of the resistance value was 3%.

Example 3 A sample was obtained in the same manner as in Example 1 except that the thickness of the second layer was 90 nm and the thickness of the fourth layer was 50 nm. The transmittance of this sample at a wavelength of 550 nm is 93%,
The minimum value of the transmittance in the visible light region was 88%, and the linearity of the resistance value was 3%.

Comparative Example 1 A float glass having a size of 300 * 320 mm and a thickness of 1.1 mm and a transmittance of 92% at a wavelength of 550 nm was washed and dried to obtain a glass plate (substrate). This board is 4
The substrate was heated to 50 ° C. and a gas adjusted to have SiH 4, N 2, and O 2 was supplied to the substrate surface to form a first layer having a thickness of 25 nm and containing SiO 2 as a main component. Then the substrate is 500
Heated to ℃, vapor of C4H9SnCl3, N2, O2,
By supplying HF vapor and regulated gas of water vapor,
On the film surface of the first layer, a second layer having a thickness of 25 nm and containing SnO2 as a main component was formed.

The glass plate with a transparent conductive film thus obtained was gradually cooled to prepare a sample, and the visible light transmittance of this sample was measured by a spectrophotometer. The result of this measurement is shown by the broken line in FIG. As can be seen from the figure, the wavelength is 550 nm.
The transmittance was 90%, and the linearity of the resistance value was 4%.

Comparative Example 2 A float glass having a size of 300 * 320 mm and a thickness of 1.1 mm and a transmittance of 92% at a wavelength of 550 nm was washed and dried to obtain a glass plate (substrate). This board is 4
The substrate was heated to 50 ° C., and a gas in which SiH 4, N 2, and O 2 was adjusted was supplied to the surface of the substrate to form a first layer having a thickness of 30 nm and containing SiO 2 as a main component. Then the substrate is 500
Heated to ℃, vaporized Ti [OCH (CH3) 2] 4, N
By supplying a gas adjusted to O 2 and O 2, a second layer containing TiO 2 as a main component and having a thickness of 110 nm was formed on the film surface of the first layer. Then, while keeping the substrate at 500 ℃, C4
By supplying H9SnCl3 vapor, N2, O2 and vapor adjusted gas, the thickness of the second layer film surface is 60 nm.
A third layer containing SnO2 as the main component was deposited.

The glass plate with a transparent conductive film having a laminated structure thus obtained was gradually cooled to prepare a sample, and the visible light transmittance of this sample was measured by a spectrophotometer. The result of this measurement is shown by the chain line in FIG. As can be seen from the figure, the transmittance at a wavelength of 550 nm was 91% and the linearity of the resistance value was 3%, but the minimum value of the transmittance in the visible light region was 7%.
It was 0%.

Comparative Example 3 The same as Example 1 except that the thickness of the fifth layer of Example 1 was 50 nm. This sample has a transmittance of 91% at a wavelength of 550 nm and a minimum transmittance of 87 in the visible light region.
%, And the linearity of the resistance value was 2%.

Comparative Example 4 The same as Example 1 except that the thickness of the second layer of Example 1 was 60 nm and the thickness of the fourth layer was 20 nm. This sample had a transmittance of 90% at a wavelength of 550 nm, a minimum transmittance of 85% in the visible light region, and a linearity of resistance of 3%.

As described above, in Examples 1 to 3, the transmittance at the wavelength of 550 nm was 93% or more, and the minimum transmittance in the visible light region was 87% or more, and the linearity of the resistance value was obtained. 5% or less can be obtained, but in Comparative Examples 1 to 4, the transmittance at the wavelength of 550 nm does not reach 93% or more (Comparative Examples 1 to 4), or the minimum value of the transmittance in the visible light region is 87. It becomes less than% (Comparative Examples 2 and 4).

[0037]

As described above, according to the present invention, a glass plate with a transparent conductive film having a high visible light transmittance and a small wavelength dependency of the transmittance can be obtained. Further, according to the transparent touch panel of the present invention using the glass plate with the transparent conductive film, the visibility is good, and color display can be supported. Further, the glass plate with a transparent conductive film of the present invention can be suitably used for a surface heating element, antistatic glass and the like by utilizing its excellent optical characteristics.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of glass with a transparent conductive film according to the present invention.

FIG. 2 is a diagram showing visible light transmission characteristics of an example of the present invention and a comparative example.

FIG. 3 is a schematic configuration diagram of a transparent touch panel according to the present invention.

[Explanation of symbols]

1 ... Glass plate with transparent conductive film, 2 ... Glass plate, 3 ... First
Layer 4, 4th layer, 5th layer, 6th layer, 7th layer 5th layer
Layer, 11 ... Transparent touch panel, 12 ... First electrode plate, 13
... second electrode plate, 14 ... spacer, 16 ... transparent conductive film, 1
7 ... Substrate, 18 ... Transparent conductive film, 21 ... Liquid crystal display panel, 22, 23 ... Electrode plate, 24 ... Liquid crystal, 25 ... Substrate, 26, 27 ... Transparent conductive film, 28 ... Substrate

Claims (2)

[Claims] 1. A glass plate having a first layer composed of a thin film containing SiO2 as a main component, a second layer composed of a thin film containing SnO2 as a main component, and a third layer composed of a thin film containing TiO2 as a main component.
Layer, a fourth layer composed of a thin film containing SiO 2 as a main component, Sn
A fifth layer made of a thin film containing O2 as a main component is sequentially laminated, and the second layer has a thickness of 30 to 120 nm, the third layer has a thickness of 10 to 110 nm, and the fourth layer has a thickness of 30 to 120 n.
m, the thickness of the 5th layer was 20-30 nm, The glass plate with a transparent conductive film characterized by the above-mentioned. 2. A glass plate with a transparent conductive film according to claim 1 is used as a first electrode plate, and a flexible transparent plate provided with a transparent conductive film is used as a second electrode plate, and the first electrode is used. A transparent touch panel, characterized in that the transparent conductive film of the plate and the transparent conductive film of the second electrode plate are arranged to face each other with a predetermined gap.