TW201946778A - Transparent conductive glass capable of exhibiting excellent conductivity and good scratch resistance - Google Patents

Abstract

The present invention provides transparent conductive glass which includes: a glass substrate having a thickness of 150 [mu]m or less and having flexibility; and a transparent conductive layer which is disposed on one side of the glass substrate in a thickness direction. The surface roughness Ra of one surface of the transparent conductive layer in the thickness direction is 10 nm or less. According to the aforementioned arrangement, the transparent conductive glass can be subjected to high-temperature processing and can exhibit excellent conductivity. Since the surface roughness Ra of the one surface of the transparent conductive layer in the thickness direction is 10 nm or less, it has excellent scratch resistance.

Description

Transparent conductive glass

The present invention relates to a transparent conductive glass, and in particular to a transparent conductive glass preferably used for optical applications.

Previously, a transparent conductive film formed by forming a transparent conductive layer containing indium tin composite oxide (ITO) on a flexible resin substrate was used for optical applications such as touch panels.

For example, Japanese Patent Laid-Open No. 2017-62609 discloses a transparent conductive film including a resin film substrate, a hard coat layer, and a transparent conductive layer. In Japanese Patent Laid-Open No. 2017-62609, a hard coat layer is provided on a transparent conductive film as a layer for suppressing the scratch resistance of the transparent conductive layer.

From the viewpoint of productivity, such a transparent conductive film is manufactured by a roll-to-roll method, specifically, by sequentially stacking a hard coat layer and a transparent conductive layer on a resin film substrate.

However, ITO is crystallized by heating, thereby exhibiting excellent electrical conductivity (low resistance). In addition, the higher the heating temperature (for example, 200 ° C. or higher), the more excellent the conductivity is.

However, a polyethylene terephthalate film used as a resin film substrate is generally deformed or damaged due to a high temperature of 200 ° C or higher.

Therefore, in order to perform high-temperature processing, it has been studied to use a glass substrate having excellent heat resistance instead of the transparent resin film. That is, it has been studied to produce a transparent conductive glass film by a roll-to-roll method using a thin glass substrate (glass film) that can be wound into a roll shape.

In addition, the hard coat layer is also formed of resin, and it will be deformed due to high temperature like the resin film base material. Therefore, in the case of high temperature treatment, the hard coat layer cannot be placed between the glass base material and the transparent conductive layer . That is, a transparent conductive layer such as ITO is directly laminated on a glass substrate, which causes an abnormality in that the scratch resistance is poor.

The present invention provides a transparent conductive glass that can exhibit excellent conductivity and good scratch resistance.

The present invention [1] includes a transparent conductive glass including: a glass substrate having a thickness of 150 μm or less and having flexibility; and a transparent conductive layer disposed on one side in the thickness direction of the glass substrate; and The surface roughness Ra of one surface of the transparent conductive layer in the thickness direction is 10 nm or less.

The present invention [2] a conductive glass as the transparent aspect 1, wherein the specific resistance of the transparent conductive layer is 2.5 × 10 ^-4 Ω / cm or less.

The present invention [3] includes a transparent conductive glass such as [1] or [2], which is wound into a roll shape.

The transparent conductive glass of the present invention includes: a glass substrate having a thickness of 150 μm or less and having flexibility; and a transparent conductive layer disposed on one side in the thickness direction of the glass substrate. Therefore, the transparent conductive glass can be subjected to high-temperature processing, and can exhibit excellent conductivity. The surface roughness Ra of one surface in the thickness direction of the transparent conductive layer is 10 nm or less. Therefore, it is excellent in abrasion resistance.

1. Transparent conductive glass The transparent conductive glass 1 which is one embodiment of the transparent conductive glass of this invention is demonstrated with reference to FIG. 1-3.

In FIG. 1, the upper and lower directions on the paper surface are the up and down directions (thickness direction, first direction), the upper side of the paper surface is the upper side (thickness side, first direction side), and the lower side of the paper surface is the lower side (the other side in the thickness direction, 1st direction on the other side). The left-right direction and the depth direction of the paper surface are plane directions orthogonal to the up-down direction. Specifically, according to the direction arrow of each figure.

As shown in FIG. 1, the transparent conductive glass 1 has a film shape (including a sheet shape) having a specific thickness, extends in a specific direction (plane direction) orthogonal to the thickness direction, and has a flat upper surface and a flat lower surface.

Specifically, the transparent conductive glass 1 includes a glass substrate 2 and a transparent conductive layer 3 arranged on the glass substrate 2 (on the thickness direction side), and is preferably composed of the glass substrate 2 and the transparent conductive layer 3. .

(Glass substrate)
The glass substrate 2 is the lowermost layer of the transparent conductive glass 1, and is a supporting material that ensures the mechanical strength of the transparent conductive glass 1 and supports the transparent conductive layer 3.

The glass substrate 2 has a film shape (including a sheet shape) and is formed of transparent glass.

Examples of the glass include alkali-free glass, soda glass, borosilicate glass, and aluminosilicate glass.

The glass substrate is flexible. Specifically, the ultimate bending stress of the glass substrate 2 is, for example, 100 MPa or more, and preferably 150 MPa or more. When the ultimate bending stress of the glass substrate 2 is equal to or more than the above-mentioned lower limit, the flexibility is excellent, and even if the glass substrate 2 is wound into a roll shape, the glass substrate 2 can be prevented from being damaged.

The ultimate bending strength is measured in the following procedure.
(1) A glass substrate having a thickness T (mm) was cut into a width of 50 mm × a length of 120 mm to obtain a sample.
(2) Bend the sample so that both ends in the longitudinal direction of the sample are close to each other.
(3) Measure the distance D (mm) at both ends of the sample in the longitudinal direction when the sample breaks.
(4) The ultimate bending stress σ _M (Pa) is calculated by the following formula.
σ _M = (E × T) / D
E represents the Young's modulus (Pa) of the glass substrate.

The glass substrate 2 has transparency. Specifically, the total light transmittance (JIS K 7375-2008) of the glass substrate 2 is, for example, 80% or more, and preferably 85% or more.

The upper surface of the glass substrate 2 may be subjected to a known base treatment (priming treatment). That is, the glass substrate 2 may be provided with an undercoat layer on the upper surface.

The thickness of the glass substrate 2 is 150 μm or less, preferably 120 μm or less, and more preferably 100 μm or less. The thickness of the glass substrate 2 is, for example, 10 μm or more, and preferably 30 μm or more. When the thickness of the glass substrate 2 is equal to or less than the above-mentioned upper limit, it is excellent in flexibility and can be wound into a roll shape. Moreover, when the thickness of the glass base material 2 is more than the said lower limit, it is excellent in mechanical strength, and can suppress the damage at the time of roll-to-roll conveyance.

The thickness of the glass substrate 2 can be measured, for example, using a dial gauge (manufactured by PEACOCK, "DG-205").

(Transparent conductive layer)
The transparent conductive layer 3 is a conductive layer that is crystallized as necessary to form a transparent pattern in a subsequent step to form a desired pattern.

The transparent conductive layer 3 is the uppermost layer of the transparent conductive glass 1 and has a film shape (including a sheet shape). The transparent conductive layer 3 is disposed on the upper surface of the glass substrate 2 such that the lower surface of the transparent conductive layer 3 is in contact with the upper surface of the glass substrate 2.

Examples of the material of the transparent conductive layer 3 include at least one selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. A metal oxide of a metal. The metal oxide may further be doped with a metal atom represented by the above group, if necessary.

Specific examples of the transparent conductive layer 3 include indium-containing oxides such as indium tin composite oxide (ITO), antimony-containing oxides such as antimony tin composite oxide (ATO), and the like. An indium-containing oxide is more preferably ITO.

When the transparent conductive layer 3 includes ITO, the content of tin oxide (SnO ₂ ) is 0.5 mass% or more, and preferably 3 mass% or more, relative to the total amount of tin oxide and indium oxide (In ₂ O ₃ ). It is, for example, 15% by mass or less, and preferably 13% by mass or less. When the content of tin oxide is at least the above lower limit, the durability of the transparent conductive layer 3 can be made better. In addition, if the content of tin oxide is equal to or less than the above-mentioned upper limit, the crystal conversion of the transparent conductive layer 3 can be made easier, and the transparency or the specific resistance can be improved.

The "ITO" in this specification may be a composite oxide containing at least indium (In) and tin (Sn), and may include additional components other than these. Examples of the additional component include metal elements other than In and Sn. Specific examples include Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe, Pb, Ni, Nb, Cr, Ga, etc.

The surface roughness Ra of the upper surface (one surface in the thickness direction) of the transparent conductive layer 3 is 10 nm or less, preferably 5.0 nm or less, more preferably 3.0 nm or less, further preferably 1.0 nm or less, and, for example, 0.001 nm or more. When the surface roughness Ra of the transparent conductive layer 3 is equal to or less than the above-mentioned upper limit, the transparent conductive glass 1 can prevent scratches on the transparent conductive layer 3 from being generated, and has excellent scratch resistance. The surface roughness Ra can be measured using an atomic force microscope (manufactured by Veeco, "Nanoscope 4").

The sheet resistance of the transparent conductive layer 3 is, for example, 300 Ω / □ or less, preferably 100 Ω / □ or less, more preferably 50 Ω / □ or less, further preferably 15 Ω / □ or less, and, for example, 1 Ω / □ □ Above. The sheet resistance can be measured by a four-terminal method.

Specific resistance of the transparent conductive layer 3 of, for example, 5.0 × 10 ^-4 Ω · cm or less, preferably 2.5 × 10 ^-4 Ω · cm or less, more preferably 2.0 × 10 ^-4 Ω · cm or less, further preferably 1.5 × 10 ^-4 Ω · cm or less. Specific resistance can be measured by a four-terminal method.

The thickness of the transparent conductive layer 3 is, for example, 10 nm or more, preferably 30 nm or more, more preferably 100 nm or more, and, for example, 300 nm or less, and preferably 160 nm or less. If the thickness of the transparent conductive layer 3 is greater than or equal to the above-mentioned lower limit, the sheet resistance value of the transparent conductive layer 3 can be further reduced, so that the conductivity is excellent. When the thickness of the transparent conductive layer 3 is equal to or less than the above-mentioned upper limit, the thickness of the transparent conductive glass 1 can be reduced. The thickness of the transparent conductive layer 3 can be measured using a scanning fluorescent X-ray analyzer.

The transparent conductive layer 3 may be either amorphous or crystalline, but from the viewpoint of conductivity (low resistance), crystalline is preferred.

Whether the transparent conductive layer is amorphous or crystalline can be determined by the following method. For example, when the transparent conductive layer is an ITO layer, it is immersed in hydrochloric acid (concentration: 5% by mass) at 20 ° C for 15 minutes. After that, it was washed with water, dried, and the resistance between terminals was measured between 15 mm. In this specification, when the resistance between the terminals between 15 mm exceeds 10 kΩ after immersion, washing, and drying in hydrochloric acid (20 ° C, concentration: 5 mass%), the ITO layer is made amorphous. When the inter-terminal resistance between 15 mm is 10 kΩ or less, the ITO layer is made crystalline.

2. Method for Manufacturing Transparent Conductive Glass Next, a method for manufacturing the transparent conductive glass 1 will be described. The transparent conductive glass 1 can be manufactured by the roll-to-roll method using the manufacturing apparatus 10 shown in FIG. 2, for example.

The manufacturing apparatus 10 includes a feed-out roller 11, a lamination section 12, a heating section 13, and a take-up roller 14.

The sending-out roller 11 is a cylindrical member having a rotation shaft for sending the glass substrate 2 to the laminated section 12. The sending-out roller 11 is arrange | positioned most upstream in the conveyance direction of the glass base material 2. The feed roller 11 is connected to a motor (not shown) for rotating the feed roller 11.

The lamination unit 12 laminates the transparent conductive layer 3 on the glass substrate 2 conveyed from the delivery roller 11. The laminated portion 12 is, for example, a sputtering device. The lamination section 12 includes a target (evaporation source) 15 which is disposed on the upper side of the glass substrate 2 and faces the glass substrate 2 at a distance from the glass substrate 2.

The target 15 is formed of the above-mentioned inorganic material constituting the transparent conductive layer 3, and preferably includes ITO. When the target 15 contains ITO, from the viewpoints of durability and crystallization of the ITO layer, the tin oxide concentration of ITO is, for example, 0.5% by mass or more, preferably 3% by mass or more, and, for example, 15% by mass Hereinafter, it is preferably 13% by mass or less.

The heating section 13 heats the glass substrate 2 and the transparent conductive layer 3 laminated thereon.

The heating section 13 is disposed inside the laminated section 12. Specifically, the heating portion 13 is disposed on the lower side of the glass substrate 2 so as to face the glass substrate 2 at a distance. That is, the heating portion 13 is disposed opposite to the target 15 with respect to the glass substrate 2.

Specific examples of the heating unit 13 include an infrared heater and an oven.

The take-up roller 14 is a cylindrical member having a rotating shaft for taking up the transparent conductive glass 1 conveyed from the laminated layer portion 12. The take-up roller 14 is disposed at the most downstream position in the conveyance direction of the glass substrate 2. The winding roller 14 is connected to a motor (not shown) for rotating the winding roller 14.

First, a known or commercially available long glass substrate 2 rolled into a roll shape is prepared and set on a feed roll 11.

Furthermore, from the viewpoint of the adhesion between the glass substrate 2 and the transparent conductive layer 3, if necessary, the lower or upper surface of the glass substrate 2 may be subjected to, for example, sputtering, corona discharge, flame, ultraviolet irradiation, or electron beam. Etching treatment such as irradiation, chemical treatment, and oxidation, or primer treatment. In addition, the glass substrate 2 can be dust-removed and purified by solvent washing, ultrasonic washing, and the like.

Thereafter, the feed roller 11 and the take-up roller 14 are rotationally driven by a motor, and the glass substrate 2 is sent out from the take-out roller 11, passes through the lamination section 12, and is taken up by the take-up roller 14.

The conveyance speed of the glass substrate 2 is, for example, 0.2 m / min or more, preferably 1 m / min or more, and, for example, 10 m / min or less, and preferably 5 m / min or less.

Then, the transparent conductive layer 3 is laminated on the upper surface of the glass substrate 2 in the laminated portion 12. Specifically, a transparent conductive layer 3 is formed on the upper surface of the glass substrate 2 transferred to the buildup section 12 by a sputtering method.

The sputtering method is performed under vacuum. Specifically, from the viewpoints of suppressing reduction in sputtering rate, discharge stability, and the like, the gas pressure during sputtering is, for example, 1 Pa or less, and preferably 0.7 Pa or less.

Examples of the sputtering gas include an inert gas such as Ar. If necessary, a reactive gas such as oxygen may be used in combination. When the reactive gas is used in combination, the flow rate ratio of the reactive gas to the total flow rate ratio of the sputtering gas and the reactive gas is, for example, 0.1 flow% or more and 5 flow% or less.

The power source used in the sputtering method may be any of DC (Direct Current) power source, AC (Alternating Current) power source, MF (Medium Frequency) power source, and RF (Radio Frequency) power source. Or, it can be a combination of them.

The discharge voltage during sputtering is appropriately determined according to the transport speed of the glass substrate 2 and the pressure or power supply during sputtering. For example, it is 200 V or higher, preferably 250 V or higher, and, for example, 500 V or lower. It is preferably below 400 V.

In order to form the transparent conductive layer 3 with a desired thickness, a plurality of sputtering methods may be performed.

When the transparent conductive layer 3 is formed, the heating portion 13 is operated to heat the glass substrate 2 and the transparent conductive layer 3 formed on the upper surface thereof. Thereby, the transparent conductive layer 3 can be crystallized while the transparent conductive layer 3 is laminated on the glass substrate 2.

The heating temperature may be a temperature at which the transparent conductive layer 3 crystallizes, and is, for example, 150 ° C or higher, preferably 200 ° C or higher, more preferably 300 ° C or higher, and, for example, 500 ° C or lower, preferably 400 ° C or lower.

The heating time of the transparent conductive layer 3 is, for example, 6 seconds or more, preferably 12 seconds or more, and, for example, 5 minutes or less, and preferably 3 minutes or less.

Thereby, the transparent conductive glass 1 provided with the glass base material 2 and the transparent conductive layer 3 can be obtained. More specifically, a transparent conductive glass 1 including a glass substrate 2 and a crystallized transparent conductive layer 3 disposed on the glass substrate 2 can be obtained. In addition, as shown in FIG. 3, the transparent conductive glass 1 can be obtained as a roll body 4 wound into a roll shape.

In addition, the thickness of the transparent conductive layer 3 and its surface roughness Ra can be changed by appropriately changing the conditions (discharge voltage, gas flow rate, etc.) during sputtering, the transfer speed of the glass substrate 2, the heating temperature, and the heating time. Appropriate change to the required range.

Thereafter, if necessary, the transparent conductive layer 3 is patterned by a known etching. The etching may be performed before the transparent conductive glass 1 is wound into the roll body 4.
Alternatively, the transparent conductive glass 1 may be etched after being sent out from the roll body 4 by a roll-to-roll method, and may be wound again into a roll shape.

The pattern of the transparent conductive layer 3 is appropriately determined according to the application to which the transparent conductive glass 1 is applied, and examples thereof include an electrode pattern such as a stripe pattern or a wiring pattern.

The etching is, for example, arranging a covered portion (shielding tape, etc.) on the transparent conductive layer 3 so as to correspond to a pattern, and etching the transparent conductive layer 3 exposed from the covered portion using an etchant. Examples of the etching solution include acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, phosphoric acid, and mixed acids thereof. Thereafter, the covering portion is removed from the upper surface of the transparent conductive layer 3, for example, by peeling or the like.

If necessary, a protective film or the like is laminated on the lower surface of the transparent conductive glass 1 and then rolled together with the protective film into a roll shape.

The thickness of the obtained transparent conductive glass 1 is, for example, 10 μm or more, preferably 50 μm or more, and, for example, 150 μm or less, and preferably 100 μm or less.

The scratch hardness (pencil method) on the upper surface of the transparent conductive glass 1 (the surface on the side of the transparent conductive layer 3) is, for example, 5 H or more, and preferably 7 H or more. The scratch hardness (pencil method) can be measured in accordance with JIS K 5600-5-4.

The load on the upper surface of the transparent conductive glass 1 in the steel wool resistance test is, for example, 2.5 kg or more, and preferably 3 kg or more. The steel wool resistance test can be measured by repeatedly rubbing steel wool of # 0000 against the upper surface of the transparent conductive layer 3 10 times. Specifically, the embodiment is described in detail.

The inner diameter of the roller body 4 is, for example, 90 mm or more, preferably 160 mm or more, and, for example, 300 mm or less, and preferably 200 mm or less.

The width of the roller body 4 is, for example, 300 mm or more, preferably 500 mm or more, and, for example, 1600 mm or less, and preferably 1200 mm or less.

The transparent conductive glass 1 is used in an optical device such as an image display device. The image display device (specifically, an image display device having an image display element such as an LCD (Liquid Crystal Display) module, an organic EL (Electroluminescence) module) is provided with a transparent conductive glass In the case of 1, the transparent conductive glass 1 is used as a substrate for a touch panel, for example. As the form of the touch panel, there are various methods such as an optical method, an ultrasonic method, an electrostatic capacitance method, and a resistive film method, and they are particularly preferably used for the electrostatic capacitance type touch panel.

The transparent conductive glass 1 is a component such as a substrate for a touch panel included in an image display device, that is, it is not an image display device. That is, the transparent conductive glass 1 is a component used to make an image display device and the like, and does not include an image display element such as an LCD module, but includes a glass substrate 2 and a transparent conductive layer 3, which are distributed as separate components and can be Devices used in industry.

The transparent conductive glass 1 includes a glass substrate 2 and a transparent conductive layer 3 disposed on the upper surface of the glass substrate 2. Therefore, the transparent conductive glass 1 can crystallize the transparent conductive layer 3 at a high temperature (for example, 200 ° C. or higher) while suppressing deformation or breakage of the substrate due to high temperature. Therefore, excellent electrical conductivity can be exhibited.

In the transparent conductive glass 1, a transparent conductive layer 3 is disposed on the surface of the glass substrate 2, and the surface roughness Ra of the upper surface of the transparent conductive layer 3 is 10 nm or less. Therefore, it is excellent in abrasion resistance.

Furthermore, since the glass substrate 2 has a thickness of 150 μm or less and has flexibility, the glass substrate 2 and the transparent conductive glass 1 can be wound into a roll shape. Therefore, it can be manufactured by a roll-to-roll method and is excellent in productivity.

3. Modification Example A modification example of the embodiment shown in FIGS. 1 to 3 will be described below. In addition, these modified examples also exert the same effects as those of the above-mentioned embodiment.

(1) In the manufacturing method using the manufacturing device shown in FIG. 2, the transparent conductive layer 3 is crystallized at the same time as the transparent conductive layer 3 is laminated. For example, although not shown, an annealing step may be performed after the stacking, so that The transparent conductive layer 3 is crystallized. That is, the laminating step of the transparent conductive layer 3 and the crystallization step of the transparent conductive layer 3 may be performed separately.

The annealing step may be performed in the atmosphere, or may be performed in a vacuum.

The heating temperature during annealing is, for example, 140 ° C or higher, preferably 180 ° C or higher, and, for example, 400 ° C or lower, and preferably 300 ° C or lower.

The heating time is, for example, 30 minutes or more, preferably 60 minutes or more, and, for example, 240 minutes or less, and preferably 180 minutes or less.

(2) In the manufacturing method using the manufacturing apparatus shown in FIG. 2, the transparent conductive layer 3 is laminated on the glass substrate 2 by a sputtering method, but for example, the transparent conductive layer 3 may be transparent by a dry method other than the sputtering method. The conductive layer 3 is laminated on the glass substrate 2.

Examples of such a dry method include a physical vapor deposition method such as a vacuum vapor deposition method and an ion plating method, and a chemical vapor deposition method.
Examples

Examples and comparative examples are shown below to further specifically describe the present invention. The present invention is not limited to any Examples and Comparative Examples. In addition, specific numerical values such as the blending ratio (content ratio), physical property values, and parameters used in the following description may be replaced with the blending ratio (content ratio) and physical property values corresponding to the equivalent values described in the above-mentioned "Embodiment" , Parameters, etc. Record the upper limit (defined as "below", "not reached" value) or the lower limit (defined as "above", "exceed" value).

Example 1
Using the manufacturing apparatus shown in FIG. 2, the transparent conductive layer 3 is laminated on the glass substrate 2 by a roll-to-roll method, thereby producing a roll-shaped transparent conductive glass 1.

Specifically, a long transparent glass substrate 2 (thickness: 100 μm, manufactured by Nippon Electric Glass Co., Ltd., “G-Leaf”) was prepared to be rolled into a roll shape.

Next, the glass substrate 2 was set on a take-out roll 11, and was sent out at a conveying speed of 2.7 m / min. After passing through the sputtering device (layered part) 12, it was wound around a take-up roll 14.

In the sputtering device 12, an ITO layer (transparent conductive layer) 3 having a thickness of 30 nm is formed on the upper surface of the glass substrate 2 by a DC sputtering method. Sputtering was performed in a vacuum atmosphere with a pressure of 0.4 Pa in which 98% of argon gas and 2% of oxygen gas were introduced. The discharge voltage is set to 292 V. The target 15 is a sintered body using 90% by mass of indium oxide and 10% by mass of tin oxide. In addition, the infrared heater (heating section) 13 was operated in the sputtering device 12 to heat the glass substrate 2 and the ITO layer 3 at 350 ° C for 20 seconds to crystallize the ITO layer.

As a result, a transparent conductive glass 1 including a glass substrate 2 and an ITO layer 3 and wound in a roll shape is manufactured.

Examples 2 to 4
A transparent conductive glass was produced in the same manner as in Example 1 except that the transfer speed and the discharge voltage were appropriately changed, and the thickness and surface roughness of the ITO layer were changed to those described in Table 1.

Examples 5 to 6
Except for appropriately changing the conveying speed, the discharge voltage, and the heating temperature, and changing the thickness and surface roughness of the ITO layer to those described in Table 1, transparent conductivity was produced in the same manner as in Example 1. glass.

Examples 7 to 8
The thickness of the transparent glass substrate 2 was changed to 50 μm. In addition, the heating temperature in the sputtering device was changed to 150 ° C, and an amorphous ITO layer was laminated on the glass substrate, and then annealed at 200 ° C for 180 minutes in the atmosphere, thereby crystallizing the ITO layer. The thickness and surface roughness of the transparent conductive layer were changed to those described in Table 1. Except for the above, a transparent conductive glass was produced in the same manner as in Example 1.

Comparative Examples 1 to 3
A transparent conductive glass was produced in the same manner as in Example 1 except that the transfer speed and the discharge voltage were appropriately changed, and the thickness and surface roughness of the ITO layer were changed to those described in Table 1.

Comparative Example 4
A cycloolefin polymer (thickness: 28 μm, manufactured by Rihon Co., Ltd., "ZEONOR") was prepared as a transparent substrate, and the heating temperature of the heating section was set to 60 ° C and the annealing temperature was set to 150 ° C. A transparent conductive resin film was produced in the same manner as in Example 7.

(Evaluation)
The physical properties of the transparent conductive glass of each Example and Comparative Example (wherein Comparative Example 4 uses a transparent conductive resin film) were evaluated in the following manner. The results are shown in Table 1.

(Ultimate bending strength of glass substrate)
The ultimate bending strength of the glass substrate (thickness T: 100 μm, 50 μm) used in each example and each comparative example was measured in the following procedure.
(1) The glass substrate was cut into a width of 50 mm × a length of 120 mm, and was set as sample 20.
(2) As shown in FIG. 4, the longitudinal end portions 21 of the sample 20 are fixed to the jig 22, and the longitudinal end portions 21 of the sample 20 are gradually brought closer to each other.
(3) The distance D between both ends 21 in the longitudinal direction of the sample when the sample 20 is broken is measured.
(4) The ultimate bending stress σ _{M is} calculated by the formula “σ _M = (E × T) / D”. In addition, E represents the Young's modulus of the glass substrate and is 73000 MPa.

As a result, when the thickness is 100 μm, the ultimate bending stress of the glass substrate is 170 MPa, and when the thickness is 50 μm, the ultimate bending stress of the glass substrate is 350 MPa.

(Surface roughness)
In the transparent conductive glass of each example and each comparative example, the surface roughness Ra of the upper surface of the ITO layer was measured using an atomic force microscope (manufactured by Veeco, "Nanoscope 4").

(Thickness of ITO layer)
The thickness of the ITO layer of the transparent conductive glass of each example and each comparative example was measured using a scanning fluorescent X-ray analyzer (manufactured by Rigaku, "ZSX PrimusII").

(Sheet resistance, specific resistance)
In accordance with JIS K7194, the four-terminal method was used to measure the sheet resistance of the ITO layer of the transparent conductive glass of each example and each comparative example. Then, the specific resistance was calculated from the sheet resistance and the thickness of the ITO layer.

(Scratch hardness obtained by pencil method)
In accordance with JIS K 5600-5-4, the scratch hardness of the transparent conductive layer of the transparent conductive glass of each example and each comparative example was measured.

(Steel wool resistance test)
Using the steel wool (SW) of # 0000, the ITO layer of the transparent conductive glass of each example and each comparative example was rubbed back and forth 10 times with a load of 10 g / cm ² to confirm whether the surface was damaged. Then, the load was changed so as to increase the load, and the occurrence of injury was confirmed in the same manner as described above. This operation is repeated until the occurrence of the injury can be confirmed, and the load at the time of the injury is shown in Table 1.

[Table 1]
Table 1

The above invention is provided as an exemplary embodiment of the present invention, and these are merely examples and should not be interpreted in a limited manner. Variations of the present invention that are clear to those skilled in the art are included in the following patent application scope.

1‧‧‧ transparent conductive glass

2‧‧‧ glass substrate

3‧‧‧ transparent conductive layer

4‧‧‧ roller

10‧‧‧Manufacturing equipment

11‧‧‧ send out roller

12‧‧‧Laminated Department

13‧‧‧Heating section

14‧‧‧ take-up roller

15‧‧‧ target

21‧‧‧ samples at both ends in the length direction

22‧‧‧Jig

D‧‧‧ The distance between the two ends of the sample in the length direction

FIG. 1 is a cross-sectional view showing an embodiment of a transparent conductive glass substrate according to the present invention.

FIG. 2 is a diagram showing the manufacturing steps of the transparent conductive glass shown in FIG. 1. FIG.

FIG. 3 is a perspective view of a roller body of the transparent conductive glass shown in FIG. 1.

FIG. 4 is a schematic diagram showing a test for measuring the flexibility of a glass substrate in an example.

Claims (3)

A transparent conductive glass, comprising: Glass substrates with a thickness of 150 μm or less and flexibility; and A transparent conductive layer disposed on one side of the glass substrate in the thickness direction; and The surface roughness Ra of one surface of the transparent conductive layer in the thickness direction is 10 nm or less. For example, the transparent conductive glass of claim 1, wherein the specific resistance of the transparent conductive layer is 2.5 × 10 ^-4 Ω · cm or less. The transparent conductive glass as in claim 1 or 2 is wound into a roll shape.