TWI486258B - Low resistance transparent transparent laminate, low resistance patterned transparent Conductive laminated body and touch panel - Google Patents

Description

Low-resistance transparent conductive laminate, low-resistance patterned transparent Conductive laminate and touch panel

The present invention relates to a low-resistance transparent conductive laminated body for a touch panel, and more particularly to a low-resistance transparent conductive laminated body comprising a transparent substrate, a transparent optical adjustment layer, a ruthenium oxide layer, and a transparent conductive layer.

In recent years, many convenient smart products have been introduced in the market, such as smart phones, touch screens, touch tablets, and e-books. With the introduction of these highly applicable touch technologies, the use of the entire touch panel has been driven. The touch panel is, for example but not limited to, a resistive touch panel or a capacitive touch panel. The touch panel is a transparent conductive laminate including a transparent organic polymer substrate and a transparent conductive film disposed on the transparent organic polymer substrate.

The transparent conductive laminate may further be patterned by a transparent conductive film to form a patterned transparent conductive laminate, wherein the patterning process removes a portion of the transparent conductive film to form a non-conductive region. The remaining portion of the transparent conductive film forms a conductive region. However, when light enters the patterned transparent conductive laminate and is reflected, since the reflectance of the transparent organic polymer substrate and the transparent conductive film is not the same, the light passing through the conductive region and the light passing through the non-conductive region Anti The difference in the rate of incidence is large, and is applied to the touch panel. When the user uses the device, the conductive area and the non-conductive area are easily and clearly seen and recognized, which in turn affects the display quality of the touch panel.

Taiwan Patent Publication No. 201213136 discloses a transparent conductive film. The transparent conductive film includes a transparent substrate, a first hard coat layer, a first transparent dielectric layer, and a first transparent conductor layer. The transparent substrate has a film thickness ranging from 2 μm to 250 μm. The film thickness of the first hard coat layer ranges from 0.5 μm to 6 μm, and the refractive index ranges from 1.40 to 1.90. The first transparent dielectric layer has a film thickness ranging from 10 nm to 50 nm and a refractive index ranging from 1.30 to 1.50. The first transparent conductor layer is patterned and has a film thickness ranging from 10 nm to 2 μm. According to the disclosure of Table 1 in the specification of the Taiwanese case, when the surface resistance value of the first transparent conductor layer after crystallization is 270 Ω/sq or more, the reflection of the light passing through the conductive region can be reduced by the regulation of the parameter conditions. The difference between the rate and the reflectance of the light passing through the non-conductive region makes it difficult for the user to see the conductive region and the non-conductive region when using the device to achieve a non-patterning effect. However, due to the increasing size of the touch panel, if the surface resistance of the first transparent conductor layer is too high, it is easy to generate noise when applied to a large touch panel. However, in order to avoid the generation of noise, by increasing the thickness of the first transparent conductor layer to lower the surface resistance value, the difference between the reflectance of the light passing through the conductive region and the reflectance of the light passing through the non-conductive region is increased, resulting in a difference. When the user views the touch panel, the conductive area and the non-conductive area are easily seen and distinguished.

In view of the above, the transparent conductive film is modified to reduce the reflectance of light passing through the conductive region and the reflection of light passing through the non-conductive region. The difference in rate is to solve the problem that the user can easily see the trace of the transparent conductive layer when viewing the touch panel, and then improve the display quality of the touch panel, which is still a problem that can be further broken by those skilled in the art.

Accordingly, a first object of the present invention is to provide a low-resistance transparent conductive laminated body in which no interference fringes are generated after light is reflected.

Therefore, the low-resistance transparent conductive laminated body of the present invention comprises: a transparent substrate; a transparent optical adjustment layer disposed on the transparent substrate and having a thickness ranging from 50 nm to 4,000 nm, and a refractive index ranging from 1.58 to 1.70; a layer disposed on the transparent optical adjustment layer and having a thickness ranging from 23 nm to 27 nm; and a transparent conductive layer disposed on the yttrium oxide layer and having a thickness ranging from 20 nm to 25 nm, and a surface resistance value ranging from less than 200 Ω/ Sq; wherein the absolute value of the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer is 0.05 or less, and the yttrium oxide is represented by the formula (I); SiO _x formula (I)

In the formula (I), x represents more than 1.6 to less than 2.0.

A second object of the present invention is to provide a low-resistance patterned transparent conductive laminated body in which no interference fringes are generated after light reflection, and a trace of patterning of a transparent conductive layer is not easily seen by a user when viewed.

The low-resistance patterned transparent conductive laminate body of the present invention comprises: a transparent substrate; a transparent optical adjustment layer disposed on the transparent substrate, and having a thickness ranging from 50 nm to 4,000 nm, and a refractive index ranging from 1.58 to 1.70; a ruthenium oxide layer disposed on the transparent optical adjustment layer and having a thickness ranging from 23 nm to 27 nm; and a patterned transparent conductive layer disposed on the ruthenium oxide layer and having a thickness ranging from 20 nm to 25 nm, and surface resistance The value ranges from less than 200 Ω/sq; wherein the absolute value of the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer is 0.05 or less, and the yttrium oxide is represented by the formula (I), SiO _x Formula (I)

In the formula (I), x represents more than 1.6 to less than 2.0.

A third object of the present invention is to provide a touch panel having better display quality.

Therefore, the touch panel of the present invention comprises the above-mentioned low-resistance transparent conductive laminated body or the above-mentioned low-resistance patterned transparent conductive laminated body.

The effect of the present invention is that the low-resistance transparent conductive laminated body of the present invention has no interference pattern generation through the regulation of the parameter conditions, and the low-resistance patterned transparent conductive laminated body formed by the low-resistance transparent conductive laminated body When the touch panel is used, the user does not easily see the trace of the transparent conductive layer during viewing, which in turn makes the touch panel have better display quality.

The following is a detailed description of the present invention: The low-resistance transparent conductive laminated body of the present invention comprises: a transparent substrate; a transparent optical adjustment layer disposed on the transparent substrate and having a thickness ranging from 50 nm to 4,000 nm, and refraction The rate ranges from 1.58 to 1.70; the ruthenium oxide layer is disposed on the transparent optical adjustment layer and has a thickness ranging from 23 nm to 27 nm; and a transparent conductive layer is disposed on the ruthenium oxide layer and has a thickness ranging from 20 nm to 25 nm. And the surface resistance value ranges from less than 200 Ω/sq; wherein the absolute value of the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer is 0.05 or less, and the yttrium oxide is determined by the formula (I) Show; SiO _x formula (I)

In the formula (I), x represents more than 1.6 to less than 2.0.

In the present invention, the absolute value of the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer is 0.05 or less, so that the interface between the transparent substrate and the transparent optical adjustment layer does not cause reflection to reduce the interference pattern. The production. At the same time, through the adjustment of the parameter conditions, when the low-resistance patterned transparent conductive laminated body is applied to the touch panel, the user does not easily see the trace of the transparent conductive layer during viewing, and then the touch panel has a comparative Good display quality.

Preferably, the low-resistance transparent conductive laminate of the present invention further comprises a functional layer disposed on the transparent substrate opposite to the transparent optical adjustment layer.

The preparation method of the low-resistance transparent conductive laminated body of the invention can be A method of preparing a low-resistance transparent conductive laminated body for a touch panel can be used. For example, the method for preparing a low-resistance transparent conductive laminated body of the present invention comprises the steps of: providing a transparent substrate; forming a transparent optical adjustment layer on the transparent substrate to obtain a first laminated body; and the first laminated body A ruthenium oxide layer is formed on the transparent optical adjustment layer to obtain a second laminate; and a transparent conductive layer is formed on the ruthenium oxide layer of the second laminate to obtain the low-resistance transparent conductive laminate of the present invention.

The method of forming the transparent optical adjustment layer is not particularly limited. The formation method is, for example but not limited to, a roll coating method, a spin coating method, or a dip coating method. From the viewpoint of continuous production, preferably, the formation method is a roll coating method.

The method of forming the ruthenium oxide layer is not particularly limited. The formation method is, for example but not limited to, a dry coating method, a wet coating method, or the like. The dry coating method is, for example but not limited to, a vapor deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method, or a plating method. Preferably, the dry coating method is a sputtering method from the viewpoint of continuous production. The wet coating method is, for example but not limited to, a roll coating method, a spin coating method, or a dip coating method. Preferably, the wet coating method is a roll coating method from the viewpoint of continuous production.

The method of forming the transparent conductive layer is not particularly limited. The formation method is, for example but not limited to, an evaporation method, a sputtering method, an ion plating method, a chemical vapor deposition method, or a plating method. From the viewpoint of effectively controlling the thickness of the transparent conductive layer, preferably, the formation method is an evaporation method or a sputtering method.

The method for preparing the low-resistance transparent conductive laminated body of the present invention further comprises a pair of the transparent conductive layer being subjected to an annealing treatment step to make the transparent conductive The layer is crystallized and its resistance value is adjusted, wherein the annealing treatment has an operating temperature ranging from 100 ° C to 200 ° C.

The method for producing a low-resistance transparent conductive laminated body of the present invention further comprises the step of forming a functional layer on the transparent substrate opposite to the transparent optical adjustment layer. The method of forming the functional layer is not particularly limited. The formation method is, for example, but not limited to, a roll coating method, a spin coating method, a dip coating method, a bar coating method, or a gravure coating method.

The method for preparing a low-resistance patterned transparent conductive laminated body of the present invention comprises the above-mentioned method for preparing a low-resistance transparent conductive laminated body, and applying a patterning treatment to the transparent conductive layer of the low-resistance transparent conductive laminated body to form a pattern The transparent conductive layer of the present invention can obtain the low-resistance patterned transparent conductive laminate of the present invention, wherein the annealing treatment step can be performed after forming the transparent conductive layer or after patterning the transparent conductive layer.

The patterning process removes a portion of the transparent conductive layer to form a non-conductive region, and the remaining portion of the transparent conductive layer forms a conductive region. The patterning process is, for example but not limited to, a dry etching method or a wet etching method.

Hereinafter, the transparent substrate, the transparent optical adjustment layer, the hafnium oxide layer, the transparent conductive layer, and the functional layer will be described in detail.

<<Transparent substrate>>

The material of the transparent substrate in the present invention is not particularly limited, and is not limited to, for example, a polyester-based resin or a polycarbonate-based resin. The polyester resin is, for example, but not limited to, polyethylene terephthalate (PET). The polycarbonate resin is, for example but not limited to In polycarbonate (referred to as PC). Preferably, the transparent substrate is made of polyethylene terephthalate.

Preferably, in the present invention, the transparent substrate has a refractive index ranging from 1.58 to 1.80. When the refractive index of the transparent substrate is less than 1.58, after the transparent conductive layer is patterned, the reflectance of the light passing through the formed conductive region and the reflectance of the light passing through the formed non-conductive region are more different. When the touch panel is used, the user can easily see the trace of the transparent conductive layer during viewing.

The thickness of the transparent substrate in the present invention is not particularly limited, and preferably, the thickness of the transparent substrate ranges from 2 μm to 300 μm; more preferably, from 10 μm to 250 μm. When the thickness of the transparent substrate is less than 2 μm, there is a problem that mechanical strength is insufficient, which makes subsequent process operations difficult. When the thickness of the transparent substrate is more than 300 μm, the manufacturing cost increases, and the total light transmittance of the low-resistance transparent conductive laminated body or the low-resistance patterned transparent conductive laminated body is lowered, and the thinning of the technology product cannot be satisfied. Demand.

<<Transparent optical adjustment layer>>

A transparent optical adjustment layer is disposed on the transparent substrate and has a thickness ranging from 50 nm to 4,000 nm, and a refractive index ranging from 1.58 to 1.70. When the thickness of the transparent optical adjustment layer is less than 50 nm, the thickness uniformity is not easily controlled. When the thickness of the transparent optical adjustment layer is more than 4,000 nm, the manufacturing cost increases. Preferably, the transparent optical adjustment layer has a thickness ranging from 50 nm to less than 500 nm.

When the refractive index of the transparent optical adjustment layer is greater than 1.70, then It is easy to control the absolute value range of the difference in refractive index between the transparent substrate and the transparent substrate to 0.05 or less, which in turn easily causes the generation of interference fringes. When the refractive index of the transparent optical adjustment layer is less than 1.58, the refractive index of the first laminate cannot be increased. Therefore, after the transparent conductive layer is patterned, the reflectance and the passage of the light passing through the formed conductive region are formed. The difference in reflectance of the light in the non-conductive area is large, and when applied to the touch panel, the user can easily see the trace of the patterning of the transparent conductive layer when viewing. Preferably, the transparent optical adjustment layer has a refractive index ranging from 1.63 to 1.68.

Preferably, the transparent optical adjustment layer is formed by a composition for forming a transparent optical adjustment layer comprising metal oxide fine particles and a functional component, wherein the functional component comprises a photohardenable adhesive and light-emitting Starting agent. The metal oxide fine particles are, for example but not limited to, titanium oxide or zirconium oxide. Preferably, the metal oxide fine particles have a refractive index ranging from 2.0 to 3.0. Preferably, the metal oxide fine particles have an average particle diameter ranging from 5 nm to 20 nm. Preferably, the metal oxide fine particles are contained in an amount ranging from 2 parts by weight to 50 parts by weight based on 100 parts by total of the total of the functional components. The photohardenable binder is, for example but not limited to, a polyfunctional monomer having a (meth)acryl group, an oligomer having a (meth)acryl group, or a polymer having a (meth)acryl group. The photoinitiator can be used for photocuring the photohardenable adhesive, and the photoinitiator can be used alone or in combination, such as but not limited to vinyl benzophenones, benzophenone derivatives. , Michlerone, Benzyne, benzyl derivative, benzoin derivative, benzoin methyl ether, α-methoxyl ester, thioxanthone and anthraquinone. Preferably, the photoinitiator is present in an amount ranging from 0.1% by weight based on 100% by weight of the total of the functional components. Up to 10% by weight.

<<Oxide layer>>

The ruthenium oxide layer is disposed on the transparent optical adjustment layer and has a thickness ranging from 23 nm to 27 nm. When the thickness of the ruthenium oxide layer is more than 27 nm, the b* value in the penetration color of the ruthenium oxide layer becomes large, and a yellow tone is obtained. When the thickness of the yttrium oxide layer is less than 23 nm, the total light transmittance of the low-resistance transparent conductive laminated body or the low-resistance patterned transparent conductive laminated body is lowered. The oxygen content of the ruthenium oxide layer can be adjusted by controlling the amount of oxygen introduced during preparation. When x in the formula (I) is 1.6 or less, the transparency of the ruthenium oxide layer is poor due to incomplete oxidation, which in turn results in a total light transmittance of the low-resistance transparent conductive laminate or the low-resistance patterned transparent conductive laminate. The difference between the reflectance of the light passing through the conductive region and the reflectance of the light passing through the non-conductive region is increased. When applied to the touch panel, the user can easily see the trace of the transparent conductive layer during viewing. Since the maximum value of _x in SiO _x is 2.0 in nature, if the amount of oxygen is further increased, the sputtering rate is lowered, resulting in a decrease in productivity.

<<Transparent Conductive Layer>>

The material of the transparent conductive layer may be used singly or in combination, and the material of the transparent conductive layer is, for example but not limited to, indium oxide, tin oxide, titanium oxide, aluminum oxide, zinc oxide, gallium oxide, or indium tin oxide (tin oxide and Indium tin oxide, referred to as ITO). Preferably, the transparent conductive layer is made of indium tin oxide.

When the transparent conductive layer is made of indium tin oxide, after crystallization (such as annealing treatment), tin (Sn ⁴⁺ ) replaces the position of indium (In ³⁺ ) in the crystal lattice, and emits an electron, and then Make the surface resistance worth declining. Preferably, the content of the tin dioxide ranges from 3 wt% to 10 wt%, based on 100 wt% of the total amount of the indium tin oxide. When the content of the tin dioxide is more than 10% by weight, the transparent conductive layer is not easily crystallized. More preferably, the tin dioxide content ranges from 5 wt% to 7 wt%.

According to the solid optical theory, when the transparent conductive layer is crystallized, the increased electron concentration causes the refractive index of the transparent conductive layer to decrease, and therefore, the refractive index before the crystallization is higher than that after the crystallization. Preferably, the transparent conductive layer has a refractive index ranging from 1.85 to 2.15. When the refractive index of the transparent conductive layer is lower than 1.85 or higher than 2.15, the transparent conductive layer is colored, and the transmittance is lowered, and the low-resistance patterned transparent conductive laminated body is applied to the touch panel. The user can easily see the trace of the transparent conductive layer patterning when viewing. More preferably, the transparent conductive layer has a refractive index ranging from 1.90 to 2.05.

The transparent conductive layer has a thickness ranging from 20 nm to 25 nm. When the film thickness of the transparent conductive layer is less than 20 nm, the surface resistance value is too high. When the film thickness of the transparent conductive layer is higher than 25 nm, the b ₁ * value in the penetration color of the low-resistance transparent conductive laminated body is increased to be yellowish.

<<Function layer>>

The functional layer is, for example but not limited to, a hard coat layer, an anti-glare layer, an anti-fingerprint layer, or a self-healing layer. Preferably, in the low-resistance transparent conductive laminate of the present invention, the thickness of the functional layer ranges from 1 μm to 10 μm. The hard coat layer can strengthen the hardness of the transparent substrate. When the film thickness of the functional layer is less than 1.0 μm, the pencil hardness of H or more cannot be satisfied. The thickness of the functional layer is large At 10 μm, during the process of preparing the functional layer, the film shrinks due to hardening, which causes the transparent substrate to curl, and the manufacturing cost increases.

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

<<Synthesis Example 1>>Forming a composition for a transparent optical adjustment layer

40 wt% of an acrylic ultraviolet curable resin, 20 wt% of propylene glycol methyl ether, and 35 wt% of methyl isobutyl ketone were mixed, followed by addition of 5 wt% of a photoinitiator (label: Ciba; model: IRGACURE 184) to form a functional component, and finally, 20 parts by weight of zirconia (manufactured by Daiei Chemical Industry Co., Ltd.; model: SZR-K) is dispersed in the functional component to obtain transparent optical adjustment. The layer composition is hereinafter referred to as H-1.

<<Composite example 2>>

40 wt% of an acrylic ultraviolet curable resin, 20 wt% of propylene glycol methyl ether, and 35 wt% of methyl isobutyl ketone were mixed, followed by addition of 5 wt% of a photoinitiator (label: Ciba; model: IRGACURE 184) to form a functional component, and finally, 28 parts by weight of zirconia (manufactured by Daiei Chemical Industry Co., Ltd.; model: SZR-K) is dispersed in the functional component to obtain transparent optical adjustment. The layer composition is hereinafter referred to as H-2.

<<Composite example 3>>

44 wt% of an acrylic ultraviolet curable resin and 55 wt% of methyl isobutyl ketone were mixed, followed by adding 1 wt% of a photoinitiator (manufactured by Ciba; model: IRGACURE 184) to form a functional component. Finally, 25 parts by weight of cerium oxide (manufactured by Nissan Chemical Co., Ltd.; model: MIBK-ST) is dispersed in the functional component to obtain a composition for forming a transparent optical adjustment layer, hereinafter referred to as H- 3.

<<Synthesis example 4>>

40 wt% of an acrylic ultraviolet curable resin, 20 wt% of propylene glycol methyl ether, and 35 wt% of methyl isobutyl ketone were mixed, followed by addition of 5 wt% of a photoinitiator (label: Ciba; model: IRGACURE 184) to form a functional component, and finally, 36 parts by weight of zirconia (manufactured by Daiei Chemical Industry Co., Ltd.; model: SZR-K) is dispersed in the functional component to obtain transparent optical adjustment. The layer composition is hereinafter referred to as H-4.

<<Synthesis example 5>>

40 wt% of an acrylic ultraviolet curable resin and 59 wt% of methyl isobutyl ketone were mixed, followed by adding 1 wt% of a photoinitiator (manufactured by Ciba; model: IRGACURE 184) to form a functional component. Finally, 33 parts by weight of cerium oxide (manufactured by Nissan Chemical Co., Ltd.; model: MIBK-ST) is dispersed in the functional component to obtain a composition for forming a transparent optical adjustment layer, hereinafter referred to as H-5. .

<<Example 1>>

A polyethylene terephthalate transparent substrate having a thickness of 125 μm was produced using polyethylene terephthalate (manufactured by TOYOBO, trade name: A4300, abbreviated as PET). On the surface of the polyethylene terephthalate transparent substrate, a wire-bar is coated with a mixture comprising 32.5 wt% of acrylic resin and 67.5 wt% of methyl ehtyl ketone. Solution. Subsequently, the film was dried at 80 ° C for 2 minutes, and then irradiated with ultraviolet light having an exposure amount of 200 mJ/cm ² to form a hard coat layer having a thickness of 4 μm on the polyethylene terephthalate transparent substrate. .

H-1 of Synthesis Example 1 was coated on a polyethylene terephthalate transparent substrate on the opposite side to the hard coat layer by a wire bar, and then irradiated with ultraviolet light having an exposure amount of 600 mJ/cm ² . A transparent optical adjustment layer having a thickness of 1 μm was formed on the polyethylene terephthalate transparent substrate to obtain a first laminate. Thereafter, the first laminate is placed in a magnetron sputtering chamber, and the crucible is used as a target, and after the chamber vacuum is reduced to 3×10 ^-6 torr, argon and oxygen are introduced into the chamber. Wherein, the flow ratio of oxygen to argon is 0.23, and the degree of vacuum of the chamber is controlled to be 5 × 10 ^-3 torr. Using a power of 4 KW, and the temperature of the first laminate is controlled at room temperature, a ruthenium oxide layer having a thickness of 25 nm is formed on the transparent optical adjustment layer of the first laminate to obtain a second laminate. Next, indium tin oxide is used as a target, wherein the content of tin is 5 wt%, and then argon gas and oxygen gas are introduced into the cavity, wherein a flow ratio of oxygen to argon gas is 0.02, and the cavity is The degree of vacuum is controlled at 5 × 10 ^-4 torr. The low-resistance transparent conductive laminated body of the present invention can be obtained by using a power of 4 KW and controlling the temperature of the second layered body at room temperature to form a transparent conductive layer having a thickness of 25 nm on the yttrium oxide layer of the second laminated body. . Next, the low-resistance transparent conductive laminated body is cut into a size of 6 cm × 6 cm, and vertically immersed in a 5 wt% hydrochloric acid solution, and immersed for 3 minutes to remove a part of the transparent conductive layer to form a conductive region and a non-conductive region. Then, the patterned transparent conductive layer was annealed in an oven at 150 ° C for 1 hour to obtain a low-resistance patterned transparent conductive laminate of the present invention.

<<Examples 2 to 8 and Comparative Examples 1 to 9>>

Examples 2 to 8 and Comparative Examples 1 to 9 were prepared in the same manner as in Example 1 to prepare a low-resistance transparent conductive laminated body and a low-resistance patterned transparent conductive laminated body, as shown in Table 1 and Table 2, respectively. .

<<Example 9>>

In the same manner as in the first embodiment, a low-resistance transparent conductive laminated body and a low-resistance patterned transparent conductive laminated body are prepared, except that indium tin oxide is used as a target when preparing a transparent conductive layer. Wherein, the content of tin is 5 wt%, after which argon gas and oxygen gas are introduced into the cavity, wherein the flow ratio of oxygen to argon is 0.01, and the vacuum degree of the cavity is controlled at 5×10 ^-4 torr . Using a power of 4 KW, and the temperature of the second laminate was controlled at room temperature, a transparent conductive layer having a thickness of 25 nm was formed on the ruthenium oxide layer of the second laminate.

<<Comparative Example 10>>

In Comparative Example 10, a low-resistance transparent conductive laminated body and a low-resistance patterned transparent conductive laminated body were prepared in the same manner as in Example 1, except that the transparent conductive layer was not subjected to annealing treatment.

<<Evaluation project>>

Refractive index and thickness measurement:

<Refractive index and thickness of transparent optical adjustment layer>

(1) The composition for forming a transparent optical layer of Synthesis Examples 1 to 5 is applied to the surface of the substrate by a wire-bar using a product name "A4300", manufactured by TOYOBO, PET as a substrate. The film was dried at 80 ° C for 2 minutes, and hardened and dried with UV energy of 200 mJ/cm ² to form a transparent optical adjustment layer.

(2) The refractive index was measured by a known Abbe refractometer manufactured by Atago.

(3) The thickness of the transparent optical adjustment layer was observed and measured in a cross section by a transmission electron microscope (Model: JEM-2100F) manufactured by JEOL.

<Refractive index and thickness of transparent conductive layer>

Si wafer was used as the substrate, ITO sputtering was completed, and the Si wafer with ITO on the surface was placed in a hot air oven, baked at 150 ° C for 60 min, and then crystallized. Then, an ellipsometer (Ellipsomete) manufactured by Sopra Corporation was used. ; model; GES 5) for refractive index determination. The thickness of the transparent conductive layer was observed and measured in a cross section by a transmission electron microscope (Model: JEM-2100F) manufactured by JEOL.

Determination of the ratio of bismuth to oxygen in the ruthenium oxide layer: using an energy dispersive spectrometer (manufactured by Oxford Corporation; model: Inca Energy), measuring the atomic ratio of yttrium and oxygen in the yttrium oxide layer, x = ( The number of oxygen atoms / the number of cesium atoms).

Penetration color measurement: The low-resistance patterned transparent conductive laminates of Examples 1 to 9 and Comparative Examples 1 to 10 were respectively measured by JIS Z 8722 standard and using a spectroscopic spectrometer (label: Hitachi; model: U4100) Measurement, the blue-yellow sensibility index of the L*a*b* color system defined in JIS b* is the benchmark.

Total light transmittance (unit: TT%) Measurement: The low-resistance patterned transparent conductive laminated bodies of Examples 1 to 9 and Comparative Examples 1 to 10 were respectively measured by the JIS K 7105 standard method and using the Japanese Electric Color Industry ( The measuring instrument (model NDH-2000) manufactured by the company was measured.

Surface resistance value (unit: Ω/sq) Measurement: The low-resistance patterned transparent conductive laminates of Examples 1 to 9 and Comparative Examples 1 to 10 were respectively measured by the JIS K 7194 standard method and using Mitsubishi Oil Chemicals Co., Ltd. The manufactured four-terminal measuring instrument (model: Loretest AMCP-T400 MCP-T610) was measured.

Reflectance (unit: %) difference measurement: The low-resistance patterned transparent conductive laminates of Examples 1 to 9 and Comparative Examples 1 to 10 were respectively placed on a spectroscopic spectrometer (brand: Hitachi; model: U4100) The light was aligned on the conductive area for measurement, and 380 nm was used as the initial measurement wavelength and irradiated, and measured to 780 nm, and the reflection intensity of each wavelength was recorded to obtain a reflection spectrum (A _k ). Next, the light is directed at the non-conductive region and then measured as described above to obtain a reflection spectrum (B _k ). The reflectance difference ΔR is obtained by the following equation:

n: total number of measurements; A _k and B _k : reflection spectrum.

Interference pattern evaluation: The low-resistance transparent conductive laminated bodies of Examples 1 to 9 and Comparative Examples 1 to 10 were placed on an appearance inspection table, and the fluorescent lamp was turned on so that the center illumination was 2000 LUX or more, and the visual angle was observed by the human eye. The angle of 45° to 60°, the detection distance is 50cm to 100cm, and the evaluation method is as follows: ○: no rainbow phenomenon; X: rainbow phenomenon.

Pattern evaluation: 16 black tapes were respectively attached to the hard coat layers of the low-resistance patterned transparent conductive laminates of Examples 1 to 9 and Comparative Examples 1 to 10, and then patterned by visual observation by a human eye. Transparent conductive layer, and confirm whether the conductive area and non-conductive area can be distinguished, the evaluation method is as follows: ◎: the conductive area and the non-conductive area cannot be distinguished; ○: the conductive area and the non-conductive area are slightly discernible; X: distinguishable Conductive and non-conductive areas.

It can be seen from the data results of Table 1 that the low-resistance transparent conductive laminated body of the present invention has no interference pattern generated by the regulation of the parameter conditions, and the low-resistance patterned transparent conductive formed by the low-resistance transparent conductive laminated body. Under the observation of the human eye, the laminated body is difficult to distinguish the conductive area and the non-conductive area of the patterned transparent conductive layer, effectively improving and alleviating the obvious problem of the patterning trace of the transparent conductive layer existing in the past, and then the touch panel can be made Better display quality.

From the data results of Table 2, the refractive indices of the transparent optical adjustment layers of Comparative Examples 1 to 3 and 5, and the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer are not within the design range of the present invention. The obtained low-resistance transparent conductive laminated body has the occurrence of interference fringes, and the low-resistance patterned transparent conductive laminated body formed therefrom has a remarkable patterning trace under the observation of the human eye.

In Comparative Example 4, although the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer is within the design range of the present invention, the refractive index of the transparent optical adjustment layer is not within the design range of the present case, although the obtained The low-resistance transparent conductive laminated body has no interference pattern, but the low-resistance patterned transparent conductive laminated body formed by the low-resistance transparent conductive laminated body has a remarkable patterning trace under the human eye observation.

The refractive indices of the transparent optical adjustment layers of Comparative Examples 6 and 7 and the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer are within the design range of the present case, but the thickness of the ruthenium oxide layer is not in this case. Within the scope of the design, although the obtained low-resistance transparent conductive laminated body can be produced without interference fringes, the low-resistance patterned transparent conductive formed by the low-resistance pattern The laminate has significant patterning marks under human observation.

The refractive index of the transparent optical adjustment layer of Comparative Example 8 and the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer are within the design range of the present case, but the proportion of oxygen in the ruthenium oxide layer is not in this case. Within the scope of the design, although the obtained low-resistance transparent conductive laminated body can be produced without interference fringes, the low-resistance patterned transparent conductive laminated body formed therefrom has remarkable patterning under human eye observation. trace.

The refractive index of the transparent optical adjustment layer of Comparative Example 9, and the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer are within the design range of the present case, but the thickness of the transparent conductive layer is not in the design of the present case. In the range, the obtained low-resistance transparent conductive laminated body can be produced without interference fringes, but the low-resistance patterned transparent conductive laminated body formed therefrom has a remarkable patterning trace under the human eye observation.

The refractive index of the transparent optical adjustment layer of Comparative Example 10, and the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer are within the design range of the present case, but the surface resistance value and thickness of the transparent conductive layer are not In the scope of the design of the present invention, although the obtained low-resistance transparent conductive laminated body can be produced without interference fringes, the low-resistance patterned transparent conductive laminated body formed by the present invention has remarkable visibility under human eyes. Patterned traces.

In summary, through the regulation of the parameter conditions, the low-resistance transparent conductive laminated body of the present invention has no interference pattern generation, and the low-resistance patterned transparent conductive laminated body formed by the low-resistance transparent conductive laminated body is in the human eye. Observed, it is not easy to see the traces of the transparent conductive layer patterning, applied to When the touch panel is used, the touch panel can be made to have better display quality, so that the object of the present invention can be achieved.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

Claims (13)

A low-resistance transparent conductive laminated body comprising: a transparent substrate; a transparent optical adjustment layer disposed on the transparent substrate and having a thickness ranging from 50 nm to 4,000 nm, and a refractive index ranging from 1.58 to 1.70; a ruthenium oxide layer, The transparent optical adjustment layer is disposed on the transparent optical adjustment layer, and has a thickness ranging from 23 nm to 27 nm; and a transparent conductive layer disposed on the ruthenium oxide layer and having a thickness ranging from 20 nm to 25 nm, and a surface resistance value ranging from less than 200 Ω/sq; Wherein, the absolute value of the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer is 0.05 or less, and the yttrium oxide is represented by the formula (I); SiO _{x is the} formula (I) (I) In the formula, x represents greater than 1.6 to less than 2.0. The low-resistance transparent conductive laminate according to claim 1, wherein the transparent optical adjustment layer has a refractive index ranging from 1.63 to 1.68. The low-resistance transparent conductive laminate according to claim 1, wherein the transparent optical adjustment layer has a thickness ranging from 50 nm to less than 500 nm. The low-resistance transparent conductive laminate according to claim 1, wherein the transparent substrate has a refractive index ranging from 1.58 to 1.80. The low-resistance transparent conductive laminate according to claim 1, wherein the transparent conductive layer has a refractive index ranging from 1.85 to 2.15. The low-resistance transparent conductive laminate according to claim 1, further comprising a functional layer disposed on the transparent substrate opposite to the transparent optical adjustment layer. A low-resistance patterned transparent conductive laminate body comprising: a transparent substrate; a transparent optical adjustment layer disposed on the transparent substrate and having a thickness ranging from 50 nm to 4,000 nm, and a refractive index ranging from 1.58 to 1.70; a ruthenium layer disposed on the transparent optical adjustment layer and having a thickness ranging from 23 nm to 27 nm; and a patterned transparent conductive layer disposed on the yttrium oxide layer and having a thickness ranging from 20 nm to 25 nm, and a surface resistance value range less than 200Ω / sq; wherein the absolute value of the range of difference in refractive index of the transparent substrate and the transparent optical adjustment layer is 0.05 or less, and the silicon oxide is represented by the formula (I) shown; SiO _x of formula (I) In the formula (I), x represents more than 1.6 to less than 2.0. The low-resistance patterned transparent conductive laminate according to claim 7, wherein the transparent optical adjustment layer has a refractive index ranging from 1.63 to 1.68. The low-resistance patterned transparent conductive laminate according to claim 7, wherein the transparent optical adjustment layer has a thickness ranging from 50 nm to less than 500 nm. a low-resistance patterned transparent conductive laminate as described in claim 7 The transparent substrate has a refractive index ranging from 1.58 to 1.80. The low-resistance patterned transparent conductive laminate according to claim 7, wherein the transparent conductive layer has a refractive index ranging from 1.85 to 2.15. The low-resistance patterned transparent conductive laminate according to claim 7, further comprising a functional layer disposed on the transparent substrate opposite to the transparent optical adjustment layer. A touch panel comprising the low-resistance transparent conductive laminate according to claim 1 or the low-resistance patterned transparent conductive laminate according to claim 7.